Curable polyorganosiloxane composition containing phosphonium salt, method for preparing the same, and use thereof

Abstract

A composition containing a phosphonium catalyst, a polyorganohydrogensiloxane, and a hydrocarbonoxy-functional organosilicon compound. The composition is curable by a method including heating. This composition and method are useful for preparing polyorganosiloxane products such as coatings, adhesives, elastomers, and foams.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 352,312, filed on June 15, 2022, under 35 U.S.C. § 119(e). U.S. Provisional Patent Application No. 63 / 352,312 is incorporated herein by reference in its entirety.

[0002] S curable polyorganosiloxane compositions, and methods for their preparation and curing are provided. More particularly, the curable polyorganosiloxane compositions include a phosphonium catalyst, a polyorganohydrogensiloxane, and a hydrocarbonoxy - functional organosilicon compound.

[0003] Introduction Silyl hydrides (Si-H) and silyl ethers (Si-OR, where R is, for example, methyl) are known to react in the presence of strong Lewis acid catalysts (known as the Piers-Rubinsztajn (「PR」) reaction) to produce siloxanes and R-H. The use of the PR reaction may be desirable for curing siloxanes in coating, adhesive, elastomer, and foaming applications. However, these reactions are well-known to be rapid. Thus, PR reaction systems are typically two-component systems where the catalyst is held apart from the Si-OR until the reaction is desired. PR-type reaction components provide storage stability for storage, but it is desirable to be able to store them together in a one-component system in such a way that they have a way to initiate (trigger) the PR-type reaction when it is desired to cure the system. There are systems where the Lewis acid catalyst is complexed with an ultraviolet (UV) light-sensitive blocker that prevents the PR-type reaction from becoming possible until the Lewis acid catalyst is irradiated with UV light. However, such systems need to be stored in the dark for storage stability and must be exposed to UV light to initiate curing. The release of the Lewis acid upon exposure to UV light tends to be slow, resulting in a reaction that starts slowly upon exposure to UV light. The application of the UV-blocked Lewis acid requires triggering a thin film such that the UV light can effectively penetrate into the composition and achieve a high surface area exposure. Thus, there is a desire for a composition that does not need to be kept shielded from UV light exposure prior to initiating the Lewis acid-catalyzed reaction, does not require rapid initiation (rapid release of the Lewis acid) of the reaction, and / or does not require the ability to rapidly trigger the reaction in the bulk composition, where the UV-blocking of the Lewis acid has drawbacks. Summary of the Invention

[0004] The curable polyorganosiloxane composition (composition) comprises (A) a phosphonium catalyst, (B) a polyorganohydrogensiloxane, and (C) a hydrocarbonoxy-functionalized organosilicon compound. A method for preparing and curing the composition is provided. Detailed Description of the Invention

[0005] The above composition can be a one - component composition. The composition contains (A) a phosphonium catalyst, (B) a polyorganohydrogensiloxane, and (C) a hydrocarbonoxy - functional organic silicon compound. The phosphonium catalyst contains a cationic salt of phosphorus and a non - coordinating anion.

[0006] Starting material (A) phosphonium catalyst The starting material (A) used here is a phosphonium catalyst containing (i) a tetravalent monocation of phosphorus and (ii) a non - coordinating anion. The tetravalent monocation of phosphorus has the formula (i - 1): [PR 1 3R 2 + which is a Lewis acidic phosphorus cation, where each R 1 is an independently selected aryl halide group, and each R 2 is independently selected from the group consisting of a halogen atom and an electron - withdrawing group. The aryl halide group R 1 can have the following formula:

[0007]

Chemical formula

[0008] R 2 's halogen atom can be selected from the group consisting of bromine (Br), Cl, and F, or can be Cl or F. R 2 's halogen atom can be F. R 2 ​The electron-withdrawing group may contain an atom with an electronegativity of ≧ 2.5, such as carbon (C) or oxygen (O), bonded to P. Alternatively, the electron-withdrawing group may have the formula -CX’3, where X’ is a halogen atom selected from Br, Cl, or F, or is Cl or F. Alternatively, R 2 The electron-withdrawing group may have the formula -CF3. Alternatively, R 2 The electron-withdrawing group may have the formula -OR 9 wherein R 9 is alkyl or aryl. R 9 Suitable alkyl groups for R 9 can be linear, branched, cyclic, or a combination of two or more thereof. Alkyl groups are exemplified by methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched-chain isomers having 5 to 18 carbon atoms), and alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. R 9 Suitable aryl groups for R 9 can be monocyclic or polycyclic and can have pendant hydrocarbyl groups. For example, R 9 aryl groups include phenyl, tolyl, xylyl, and naphthyl, and further include aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl. Alternatively, R 9 aryl groups can be monocyclic such as phenyl, tolyl, or benzyl, or alternatively, R 9 aryl groups can be phenyl.

[0009] Alternatively, in formula (i-1), each R 1 can be a fluorinated aryl group. Alternatively, in formula (i-1), R 2 can be F. Alternatively, (i) the tetravalent monocation of phosphorus can have the formula: [P(C6F5)3F] + and can have.

[0010] (i) In addition to the tetravalent monocation of phosphorus, (A) the phosphonium catalyst further comprises (ii) a non-coordinating anion introduced above. The non-coordinating anion may have a charge that is not localized on a specific atom but is delocalized over the surface of the anion. Suitable non-coordinating anions include trifluoromethanesulfonate (triflate) of the formula [CF3SO3] - and anions of the formula [BR 3 4] - wherein each R 3 is independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups. The monovalent hydrocarbon group can be an alkyl group or an aryl group. The monovalent halogenated hydrocarbon group can be an alkyl group or an aryl group in which one or more hydrogen atoms are replaced by F, Cl, or Br.

[0011] R 3 Suitable alkyl groups for can be linear, branched, cyclic, or a combination of two or more thereof. R 3Alkyl groups suitable for [description] are exemplified by methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched-chain isomers having 5 to 18 carbon atoms). The alkyl group is further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Suitable halogenated alkyl groups include chlorinated alkyl groups such as chloromethyl group and chloropropyl group, fluorinated alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, 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, chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl and 2,3-dichlorocyclopentyl, and fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl and 3,4-difluoro-5-methylcycloheptyl, but are not limited thereto.

[0012] R 3 The aryl group suitable for [description] can be monocyclic or polycyclic and can have pendant hydrocarbyl groups. For example, the aryl group of R 3 includes phenyl, tolyl, xylyl, and naphthyl, and further includes aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl. Alternatively, the aryl group of R 3 can be monocyclic such as phenyl, tolyl, or benzyl, or the aryl group of R 3 can be phenyl. The halogenated aryl group of R 3 can be as described above for R 1 .

[0013] Alternatively, the non-coordinating anion may be completely saturated and may not have free valence electrons that participate in covalent or coordination bonds with phosphonium. The completely saturated anion may have the formula [BR 3 4] - wherein each R 3 is independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups as described above. Alternatively, each R 3 may be a halogenated aryl group. Alternatively, the anion may have the formula [B(C6F5)4] - .

[0014] Alternatively, (A) the catalyst may have the following formula:

[0015]

Chemical formula

[0016] The starting material (A) can be prepared by methods known in the art, such as those disclosed in Science 2013, 341, 1374 - 1377, by varying the appropriate starting materials. The starting material (A) used herein may be any one of the above catalysts or a combination of two or more of the above catalysts.

[0017] The composition described herein contains (A) a catalyst in an amount sufficient to cure the composition. The exact amount of the (A) catalyst depends on various factors including the selection of (B) the polyorganohydrogensiloxane, the SiH content, and the selection and amount of (C) the hydrocarbonoxy-functional organosilicon compound. However, the composition may contain a catalyst sufficient to provide a concentration of tetravalent monocation of phosphorus that can be at least 1 ppm, or at least 2 ppm, or at least 5 ppm. On the other hand, at the same time, this amount can be at most 1,000 ppm, or at most 500 ppm, or at most 100 ppm, or at most 50 ppm, each based on the total weight of the starting materials (A), (B), and (C). Alternatively, the amount of (A) the phosphonium catalyst can be from 1 ppm to 1,000 ppm, or from 2 ppm to 500 ppm, or from 5 ppm to 100 ppm, or 10 ppm, based on the total weight of (A) the catalyst, (B) the polyorganohydrogensiloxane, and (C) the hydrocarbonoxy-functional organosilicon compound in the composition.

[0018] Starting material (B) polyorganohydrogensiloxane The composition described herein further contains (B) a polyorganohydrogensiloxane. The polyorganohydrogensiloxane has at least one Si-H moiety per molecule. Alternatively, the polyorganohydrogensiloxane can have two or more Si-H moieties per molecule. A polyorganohydrogensiloxane having a plurality (e.g., two or more, or three or more) of Si-H moieties per molecule can react with a plurality of hydrocarbonoxy-functional moieties of the starting material (C) and is thus useful as a crosslinking agent in the composition described herein.

[0019] The polyorganohydrogensiloxane is HR 4 2SiO 1 / 2 、R 4 3SiO 1 / 2 、HR 4 SiO 2 / 2 、R 4 2SiO2 / 2 , R 4 SiO 3 / 2 , HSiO 3 / 2 , and SiO 4 / 2 It may contain two or more siloxane units selected from the group consisting of units, wherein each R 4 is an independently selected monovalent hydrocarbon group that does not contain aliphatic unsaturation, provided that at least one unit per molecule contains an Si-H moiety (i.e., HR 4 2SiO 1 / 2 , HR 4 SiO 2 / 2 , and HSiO 3 / 2 at least one of is present in the polyorganohydrogensiloxane). The monovalent hydrocarbon group that does not contain aliphatic unsaturation can be an alkyl group or an aryl group, as described above for R 3 . Alternatively, each R 4 can be an independently selected alkyl group. Alternatively, each R 4 can be independently selected from the group consisting of methyl and phenyl. Alternatively, each R 4 can be methyl.

[0020] Alternatively, (B) the polyorganohydrogensiloxane can be linear or cyclic. For example, (B) the polyorganohydrogensiloxane can be a linear polyorganohydrogensiloxane with the unit formula (B-1): (HR 4 2SiO 1 / 2 ) g (R 4 3SiO 1 / 2 ) h (R 4 2SiO 2 / 2 ) i (HR 4 SiO 2 / 2 ) j wherein R 4is as described above, and the subscripts g, h, i, and j have values such that g≧0, h≧0, the quantity (g + h)=2, i≧0, j≧0, and the quantity (g + j)≧1, and the quantity (i + j) is between 0 and 2,000. The quantity (i + j) can be 2,000 or less, or 1,000 or less, or 750 or less, or 500 or less, or 250 or less, or 100 or less, or 50 or less. On the other hand, at the same time, the quantity (i + j) can be 0 or more, or 1 or more, or 2 or more, or 3 or more, or 4 or more, or 5 or more, or 10 or more, or 15 or more, or 20 or more. Alternatively, the quantity (i + j) can be between 0 and 1,000, or between 1 and 500, or between 2 and 250, or between 3 and 100. Alternatively, the quantity (i + j) can be between 1 and 100. Alternatively, the quantity (i + j) can be between 2 and 50. Alternatively, the quantity (i + j) can be between 5 and 25. Alternatively, when g = 0 and h = 2, j≧1 (or ≧2). Alternatively, g can be 1 and h can be 1. Alternatively, g can be 2 and h can be 0. Alternatively, i can be between 0 and 5, or between 1 and 4, or between 2 and 4, or between 3 and 3.5. Alternatively, i can be between 5 and 25. Alternatively, j can be between 1 and 10, or between 2 and 9, or between 3 and 8, or between 4 and 7, or between 5 and 6. Alternatively, when g>0, j can be 0.

[0021] Polydiorganohydrogensiloxanes suitable for use herein are exemplified by the following: (i) α,ω-dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (ii) α,ω-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, (iii) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (iv) α,ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, and (v) α-dimethylhydrogen siloxy, ω-trimethylsiloxy terminated poly(dimethylsiloxane / methylhydrogen siloxane), (vi) α-dimethylhydrogen siloxy, ω-trimethylsiloxy terminated polymethylhydrogen siloxane, (vii) Combinations of two or more of these.

[0022] Alternatively, the polyorganohydrogen siloxane can be cyclic. The cyclic polyorganohydrogen siloxane can contain the unit formula (B-2): (R 4 2SiO 2 / 2 ) u (R 4 HSiO 2 / 2 ) v wherein R 4 is as defined above, the subscript u is 0 or more, the subscript v is 1 or more, and the quantity (u + v) is from 3 to 15. Alternatively, u can be 0. Alternatively, u can be 0 or more, or 1 or more, or 2 or more, or 3 or more. At the same time, u can be at most 6, or at most 5, or at most 4. Alternatively, u can be from 0 to 6, or from 0 to 4, or from 0 to 2, or from 1 to 6. Alternatively, v can be 1 or more, or 2 or more, or 3 or more, or 4 or more. At the same time, v can be at most 12, or at most 10, or at most 8, or at most 6, or at most 5. Alternatively, v can have an average value of 4. Alternatively, v can be from 1 to 12, or from 2 to 10, or from 3 to 8, or from 3 to 6, or from 3 to 5. In the unit formula (B-2), each R 4 can be methyl. Examples of the cyclic polyorganohydrogen siloxane include (i) trimethylcyclotrisiloxane, (ii) tetramethylcyclotetrasiloxane, (iii) pentamethylcyclopentasiloxane, (iv) hexamethylcyclohexasiloxane, and (v) combinations of two or more of these.

[0023] Suitable polyorganohydrogensiloxanes are known in the art and are commercially available. For example, DOWSIL™ 6-3570 Polymer, DOWSIL™ SH 1107 Fluids, and XIAMETER™ MHX-1107 Fluids are available from The Dow Chemical Company (Midland, Michigan, USA). Polydiorganohydrogensiloxanes, such as HMS-992 (trimethylsilyl-terminated polymethylhydrogensiloxane), HMS-HM271 (hydride-terminated methylhydrogensiloxane-dimethylsiloxane copolymer), and HMS-031 (trimethylsiloxy-terminated methylhydrogensiloxane dimethylsiloxane copolymer) are available from Gelest, Inc. (Morrisville, Pennsylvania, USA). Other polydiorganohydrogensiloxanes available from Gelest include HMS-H271, HMS-071, HMS-993, HMS-301 and HMS-301 R, HMS-991, HMS-993, HMS-082, HMS-151, HMS-013, HMS-053, HAM-301 (octyl-functionalized), and HPM-502 (phenyl-functionalized). Methods for preparing linear and branched polyorganohydrogensiloxanes suitable for use herein, such as hydrolysis and condensation of organohalosilanes, are well known to those skilled in the art as exemplified in U.S. Patent No. 3,957,713 (Jeram et al.), U.S. Patent No. 4,329,273 (Hardman, et al), U.S. Patent No. 4,370,358 (Hayes, et al.), U.S. Patent No. 4,707,531 (Shirahata), U.S. Patent No. 5,310,843 (Morita), and U.S. Patent No. 2,823,218 (Speier, et al.), which disclose organohydrogensiloxane oligomers, linear polymers, and cyclic polymethylhydrogensiloxanes.

[0024] The amount of (B) polyorganohydrogensiloxane in the composition depends on various factors including the Si-H content of the polyorganosiloxane (which can be determined using quantitative infrared analysis according to ASTM E168), as well as the type and amount of (C) hydrocarbonoxy-functional organic silicon compound, and any optional additional starting materials are present. However, the amount of (B) polyorganohydrogensiloxane in the composition can be 1 wt% or more, or 5 wt% or more, or 10 wt% or more, or 15 wt% or more, or 20 wt% or more, or 25 wt% or more, while at the same time the concentration can be <100 wt%, or 90 wt% or less, or 85 wt% or less, or 80 wt% or less, or 75 wt% or less, or 60 wt% or less, each based on the total weight of (A) catalyst, (B) polyorganohydrogensiloxane, and (C) hydrocarbonoxy-functional organic silicon compound in the composition. Alternatively, the amount of (B) polyorganohydrogensiloxane in the composition can be from 1 wt% to <100 wt%, or from 5 wt% to 90 wt%, or from 10 wt% to 85 wt%, or from 15 wt% to 80 wt%, or from 20 wt% to 75 wt%, or from 25 wt% to 70 wt%, and / or from 30 wt% to 90 wt%, each based on the total weight of (A) catalyst, (B) polyorganohydrogensiloxane, and (C) hydrocarbonoxy-functional organic silicon compound in the composition.

[0025] The polyorganohydrogensiloxane, (B), can be the same molecule as the (C-2) hydrocarbonoxy-functional organosiloxane oligomer, or polymer described below, or a different molecule. That is, the composition contains an organosiloxane oligomer, or polymer having both an Si-H moiety and a silicon-bonded hydrocarbonoxy-functional moiety, and thus the polymer, or oligomer can also contain an Si-H moiety and can function as both starting materials (B) and (C) in the composition. For example, when both an Si-H moiety and a hydrocarbonoxy moiety are present in the same molecule, the R in the formula shown above 4One or more examples of can be replaced by a hydrocarbon oxy moiety having the formula (c) shown below. Alternatively, (B) the polyorganohydrogensiloxane can be a molecule different from the (C) hydrocarbon oxy-functionalized organosilicon compound that is also present in the composition. The starting material (C) hydrocarbon oxy-functionalized organosilicon compound may not contain an Si-H moiety.

[0026] Starting material (C) hydrocarbon oxy-functionalized organosilicon compound The starting material (C) hydrocarbon oxy-functionalized organosilicon compound in the composition has a formula selected from the group consisting of (C-1) hydrocarbonoxysilane, (C-2) hydrocarbon oxy-functionalized organosiloxane oligomers, or polymers, and (C-3) combinations of (C-1) and (C-2).

[0027] The hydrocarbonoxysilane has the formula (C-1): R 7 (4-b) Si(OR 5 ) b wherein each R 7 is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, each R 5 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the subscript b is 1 to 4. The monovalent hydrocarbon group and the monovalent halogenated hydrocarbon group of R 7 are as described above for R 3 and as exemplified above. Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms of R 5 include alkyl groups such as methyl group, ethyl group, propyl group (including isopropyl group, n-propyl group), butyl group (including n-butyl group, isobutyl group, t-butyl group, sec-butyl group), as well as pentyl group, hexyl group, and branched-chain isomers having 5 to 6 carbon atoms. Alternatively, each R 5may be methyl, or ethyl, or may be methyl. Alternatively, subscript b may be 1 or more, or 2 or more, while at the same time, subscript b may be 4 or less, or 3 or less. Alternatively, subscript b may be 1 to 3, or 1 to 2, or 2 to 3, or 2 to 4.

[0028] Alternatively, the hydrocarbyloxysilane may have the formula R 7 Si(OR 5 )3, wherein R 7 , and R 5 are as described above. Alternatively, each R 7 may be an alkyl group having 1 to 20 carbon atoms, and each R 5 may be an alkyl group having 1 to 4 carbon atoms.

[0029] The starting material (C-1) hydrocarbonoxysilane may include alkoxysilanes exemplified by monoalkoxysilanes such as trialkylalkoxysilanes, dialkoxysilanes such as dialkyldialkoxysilanes, trialkoxysilanes such as alkyltrialkoxysilanes, tetraalkoxysilanes, or combinations thereof. Examples of suitable monoalkoxysilanes include trimethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triethylmethoxysilane, vinyldimethylethoxysilane, allyldimethylmethoxysilane, vinyldimethylmethoxysilane, dimethylphenylmethoxysilane, methyldiphenylmethoxysilane, triphenylmethoxysilane, and combinations thereof. Examples of suitable dialkoxysilanes include diisobutyldiethoxysilane, n-octadecylmethyldiethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, di(4-tolyl)dimethoxysilane, and combinations thereof. Examples of suitable trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, allyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, p-tolyltrimethoxysilane, p-tolyltriethoxysilane, pentafluorophenyltriethoxysilane, 4-trifluoromethyltetrafluorophenyltriethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltrimethoxysilane, benzyltriethoxysilane, and combinations thereof. Examples of suitable tetraalkoxysilanes include tetraethoxysilane and tetra-n-propoxysilane. These alkoxysilanes are known in the art and can be prepared by known methods such as the alkoxylation of the corresponding chlorosilane, and / or suitable alkoxysilanes are commercially available, for example, from Gelest, Inc. of Morrisville, Pennsylvania, USA.

[0030] Other commercially available alkoxysilanes include XIAMETER™ OFS-6070 silane, XIAMETER™ OFS-6011 silane, XIAMETER™ OFS-6020 silane, XIAMETER™ OFS-6030 silane, DOWSIL™ Z-6062 silane, DOWSIL™ Z-6300 silane, DOWSIL™ Z-6341 silane, XIAMETER™ OFS-6040 silane, DOWSIL™ Z-6023 silane, DOWSIL™ Z-6015 silane, XIAMETER™ OFS-6920 silane, XIAMETER™ OFS-6690 silane, and XIAMETER™ OFS-6076 silane, all of which are commercially available from The Dow Chemical Company of Midland, Michigan, USA.

[0031] Alternatively, the (C) hydrocarbon oxy-functionalized organosilicon compound may contain a (C-2) hydrocarbon oxy-functionalized partial organosiloxane oligomer or polymer, which contains silicon bonded to the hydrocarbon oxy-functional part of formula (c):

[0032]

Chemical formula

[0033] Alternatively, each D can be independently selected from an oxygen atom and a divalent hydrocarbon group. Alternatively, each D can be an oxygen atom. Alternatively, each D can be a divalent hydrocarbon group exemplified by an alkylene group such as ethylene, propylene, butylene, or hexylene, an arylene group such as phenylene, or

[0034] [Chemical formula] an alkylarylene group such as etc. Alternatively, an example of D can be an oxygen atom, while a different example of D can be a divalent hydrocarbon group.

[0035] Alternatively, each R X can be independently selected from the group consisting of an alkoxy group and an alkenyloxy group. Alternatively, each R X can be an alkoxy group such as methoxy or ethoxy.

[0036] Alternatively, each R in the above formula 6 can be independently selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

[0037] The organosiloxane oligomer or polymer may contain a hydrocarbon oxy-functional part of the formula shown above in an amount of 0.2 mol% or more, or 0.5 mol% or more, or 0.6 mol% or more of the oligomer or polymer. Meanwhile, the amount may be 10 mol% or less, or 5 mol% or less, or 2 mol% or less, or 1.5 mol% or less, or 1.2 mol% or less. Alternatively, the amount of the hydrocarbon oxy-functional part of the formula shown above may be 0.2 mol% to 10 mol%, or 0.5 mol% to 5 mol%, or 0.5 mol% to 2.0 mol%, or 0.5 mol% to 1.5 mol%, or 0.6 mol% to 1.2 mol%.

[0038] The starting material (C-2) may have a linear polyorganosiloxane skeleton, i.e., a polydiorganosiloxane skeleton. When the starting material (C-2) hydrocarbon oxy-functional oligomer or polymer has a polydiorganosiloxane skeleton, the starting material (C-2) may include an alkoxy endblock polydiorganosiloxane, an alkoxysilyl hydrocarbylene endblock polydiorganosiloxane, or a combination thereof.

[0039] Alternatively, the starting material (C-2) is of the formula (C-3):

[0040]

Chemical formula

[0041] Alternatively, the organosiloxane oligomer, or polymer, has the unit formula (C-4): (R X R 6 2SiO 1 / 2 ) o (R 6 3SiO 1 / 2 ) p (R 6 2SiO 2 / 2 ) q (R X R6 SiO 2 / 2 ) r (R X SiO 3 / 2 ) s (R 6 SiO 3 / 2 ) t (SiO 4 / 2 ) u may contain, wherein R X represents a group of the formula -OR 5 , and R 5 is as described above, and the subscripts o, p, q, and r are such that o≧0, p≧0, q≧0, r≧0, s≧0, t≧0, u≧0, and the quantity (o + r + s) has a value having an average value of 1 or more, or 1 to 6, or 1 to 3, or 1 to 2, and each 6 is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group as described above for R 3 . Alternatively, the quantity (o + p + q + r + s + t + u) may be at least 3, or 3 to 2,000. Alternatively, the quantity (q + r) may be 1 to 2,000, or 1 to 50. Alternatively, the quantity (o + p) may be 0 to 50, or 0 to 2. Alternatively, 1≧s≧0. Alternatively, 1≧t≧0. Alternatively, the quantity (o + r + s) has an average value of 1 to 6, or 1 to 3, or 1 to 2. Alternatively, in the above unit formula (C-4), each R 6 may be selected from the group consisting of alkyl, alkenyl, and aryl. Alternatively, the alkyl group of R 6 may be selected from the group consisting of methyl, ethyl, and propyl. Alternatively, the alkenyl group of R 6 may be selected from the group consisting of vinyl, allyl, and hexenyl. Alternatively, the aryl group of R 6 may be phenyl. Alternatively, in the above unit formula, each R X may be methoxy or ethoxy.

[0042] Alternatively, (for example, when o has an average value of 2 and p = r = s = t = u = 0), the starting material (C-2) has the formula (C-5): R 6 2RX SiO-(R 6 2SiO) b -OSiR X R 6 2 may contain a polydiorganosiloxane of the formula, wherein each R 6 , and each R X is as described above, and the subscript b is ≧1. Alternatively, the subscript b can be 1 to 2,000, or 5 to 900, or 5 to 50, or the subscript b can be 1 to 50. Alternatively, in formula (C-5), each R 6 can be independently selected from the group consisting of alkyl (e.g., methyl, ethyl, and propyl), alkenyl (e.g., vinyl, allyl, and hexenyl), and aryl (e.g., phenyl). Alternatively, in formula (C-5), each R X can be methoxy or ethoxy. The polydiorganosiloxane of formula (C-5), such as methoxy-terminated polydimethylsiloxane having a viscosity of 5 to 12 cSt, is commercially available from Gelest, Inc., and 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane is commercially available from Millipore Sigma, St. Louis, Missouri, USA.

[0043] Alternatively, the starting material (C-2) is of the unit formula C-6): (R 6 SiO 3 / 2 ) m (R 6 R X SiO 2 / 2 ) n (R 6 2R X SiO 1 / 2 ) z and may contain, wherein R 6 , and R X are as described above, the subscript m is >0 to 100, the subscript n is 0 to 100, and the subscript z is 0 to 20. Alternatively, the subscript m can be >0 to 20, or 1 to 20. Alternatively, the subscript n can be 1 to 20. Alternatively, the subscript z can be 0. Alternatively, the subscript z can be >0 to 20. Alternatively, in the unit formula (C-6), each R6 may be independently selected from the group consisting of alkyl (e.g., methyl, ethyl, and propyl), alkenyl (e.g., vinyl, allyl, and hexenyl), aryl (e.g., phenyl), and haloalkyl (e.g., chloromethyl, chloropropyl, and trifluoropropyl). Alternatively, in unit formula (C-6), each R X may be methoxy or ethoxy. Those skilled in the art will recognize that the alkoxy-functional siloxane resin may further contain a hydroxyl group. Examples of suitable alkoxy-functional siloxane resins of unit formula (C-6) include DOWSIL™ 3037, DOWSIL™ 3074, DOWSIL™ 1686, DOWSIL™ CF0189, DOWSIL™ Z-6289, DOWSIL™ US-CF2403 Resin, and DOWSIL™ 2405 Resin from Dow Silicones Corporation of Midland, Michigan, USA.

[0044] Suitable resins for starting material (C-2) and methods for their preparation are known in the art. For example, alkoxy-functional organopolysiloxane resins, or resin-polymer blends, prepared as described in U.S. Patent No. 9,670,392, U.S. Patent No. 10,125,225, or International Publication No. 2014 / 124389 may be used as starting material (C-2) described herein.

[0045] The starting material (C) may include one or more of the hydrocarbon oxy-functional organic silicon compounds described herein. The exact amount of the (C) hydrocarbon oxy-functional organic silicon compound in the composition depends on various factors, including the Si-H content of the polyorganosiloxane and the type and amount of the selected (C) hydrocarbon oxy-functional organic silicon compound. However, the amount of the (C) hydrocarbon oxy-functional organic silicon compound in the composition may be 1 wt% or more, or 2 wt% or more, or 3 wt% or more, or 4 wt% or more, or 5 wt% or more, based on the total weight of the (A) catalyst, (B) polyorganohydrogensiloxane, and (C) hydrocarbon oxy-functional organic silicon compound in the composition. At the same time, the concentration may be 90 wt% or less, or 70 wt% or less, or 50 wt% or less, or 30 wt% or less, or 15 wt% or less. Alternatively, the amount of the (C) hydrocarbon oxy-functional organic silicon compound in the composition (when the starting materials (B) and (C) are different components) may be 1 wt% to 90 wt%, or 2 wt% to 70 wt%, or 3 wt% to 50 wt%, or 4 wt% to 30 wt%, or 5 wt% to 15 wt%, or 6 wt% to 14 wt%, based on the total weight of the (A) catalyst, (B) polyorganohydrogensiloxane, and (C) hydrocarbon oxy-functional organic silicon compound in the composition, respectively.

[0046] Starting material (D) Solvent The starting material (D) is an optional solvent that can be used in the compositions and methods described herein to facilitate the combination of starting materials (A), (B), and / or (C). The solvents used herein serve to fluidize the starting materials and do not substantially react with any of these starting materials. The solvent may be selected based on the solubility of the starting materials and the volatility of the solvent. "Solubility" means that the solvent is sufficient to dissolve and / or disperse the starting material. Volatility refers to the vapor pressure of the solvent. For example, the starting material (A), a phosphonium catalyst, can be dissolved in a solvent before combining the starting material (A) with the starting materials (B) and (C). Alternatively, the starting material (B) can be dissolved in a solvent before combining it with the starting materials (A) and (C), for example, when the starting material (B) is a viscous fluid such as gum or a solid at room temperature such as a resin. Alternatively, the starting material (C) can be dissolved in a solvent before combining it with the starting materials (A) and (B), for example, when the starting material (C) is a solid at room temperature such as a resin. The solvent can be used in any amount selected by those skilled in the art depending on various factors such as the selection of the starting materials (A, (B), and (C) and their solubility, etc.).

[0047] Suitable solvents may be hydrocarbons. Suitable hydrocarbons include aromatic hydrocarbons such as benzene, toluene, or xylene, and / or aliphatic hydrocarbons such as heptane, hexane, or octane. Alternatively, the solvent can be a halogenated hydrocarbon such as chloroform, 1,1,1-trichloroethane, or methylene chloride. A single solvent, or a combination comprising two or more solvents, may be used herein.

[0048] The amount of the solvent can vary depending on various factors such as the type of solvent selected, as well as the amount and type of other starting materials selected. However, the amount of the solvent can be 0.1% by weight or more, or 2% by weight or more, based on the total weight of starting materials (A), (B) and (C). On the other hand, at the same time, the amount of the solvent can be at most 99% by weight, or at most 50% by weight. Alternatively, the amount of (D) the solvent can be 0.1% to 99% by weight, or 2% to 50% by weight, based on the total weight of (A) the catalyst, (B) the polyorganohydrogensiloxane, and (C) the hydrocarbon oxy-functionalized organosilicon compound in the composition.

[0049] The composition can include a phosphonium catalyst, a polyorganohydrogensiloxane, and a hydrocarbon oxy-functionalized organosilicon compound (and a solvent if present). Alternatively, the composition described herein can optionally further include additional components. The optional additional components can be present at a concentration of 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or even 1% by weight or less, based on the weight of the composition.

[0050] Optional additional components Examples of possible optional components include one component, or a combination of two or more components, selected from the group consisting of pigments (such as carbon black or titanium dioxide), fillers (metal oxides including SiO2) (typically at a concentration of 50% by weight or less based on the weight of the composition), moisture scavengers, optical brighteners, stabilizers (such as antioxidants and UV stabilizers), and corrosion inhibitors.

[0051] Alternatively, in addition to or instead of the above optional components, the composition can optionally further include a polyorganosiloxane that does not contain an Si-H moiety and does not contain a hydrocarbon oxy moiety. The polyorganosiloxane is R 4 3SiO 1 / 2 、R 4 2SiO2 / 2 , R 4 SiO 3 / 2 , and SiO 4 / 2 units, wherein each R 4 is an independently selected monovalent hydrocarbon radical free of aliphatic unsaturation, as defined above. Alternatively, the polyorganosiloxane can be a polydiorganosiloxane, which can be linear or cyclic. For example, a polydiorganosiloxane can be represented by the unit formula (1): (R 4 3SiO 1 / 2 )2(R 4 2SiO 2 / 2 ) x wherein R 4 is as above, and 1,000≧x≧1. Alternatively, the subscript x can be at least 1, alternatively at least 2, alternatively at least 3, alternatively at least 5, alternatively at least 10, alternatively at least 25, while at the same time, the subscript x can be up to 1,000, alternatively up to 500, alternatively up to 250, alternatively up to 100, alternatively up to 50. Alternatively, the subscript X can have a value such that 500≧x≧1, alternatively 250≧x≧2, alternatively 100≧x≧5, alternatively 50≧x≧10, and alternatively 50≧x≧25.

[0052] Polydiorganosiloxanes suitable for use herein are exemplified by the following: (i) α,ω-trimethylsiloxy-terminated polydimethylsiloxane, (ii) α,ω-dimethylphenylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane); (iii) α,ω-dimethylphenylsiloxy-terminated polymethylphenylsiloxane, (iv) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane); (v) α,ω-trimethylsiloxy-terminated polymethylphenylsiloxane, (vi) A combination of two or more of these.

[0053] Polydiorganosiloxanes are known in the art and are commercially available. For example, DOWSIL™ 200 Fluids, DOWSIL™ OS Fluids, and XIAMETER™ PMX-200 Silicone Fluids are commercially available from The Dow Chemical Company (Midland, Michigan, USA).

[0054] Alternatively, the polyorganosiloxane can be a cyclic polydiorganosiloxane containing the unit formula (2): (R 4 2SiO 2 / 2 ) y wherein R 4 is as described above, and 15 ≧ y ≧ 3. Alternatively, the subscript y can be at least 3, or at least 4, or at least 5, or at least 6, while at the same time, the subscript y can be at most 15, or at most 12, or at most 10, or at most 8, or at most 6. Alternatively, the subscript y can have a value such that 12 ≧ y ≧ 3, or 10 ≧ y ≧ 3, or 8 ≧ y ≧ 3, or 6 ≧ y ≧ 3, or 6 ≧ y ≧ 4.

[0055] Examples of cyclic polydiorganosiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and combinations of two or more thereof. Suitable cyclic polydiorganosiloxanes are commercially available, for example, from Sigma-Aldrich, Inc. (St. Louis, Missouri, USA).

[0056] Alternatively, the composition may not contain one or a combination of two or more such additional components. In addition, the composition may contain 1 wt% or less, or 0.5 wt% or less water, based on the weight of the composition. Alternatively, the composition may be water-free.

[0057] The compositions described herein may be free of transition metals. "Free of transition metals" means that the composition contains no, or an undetectable amount of, or only an insufficient amount of, the metals of Groups 3 - 12 of the IUPAC Periodic Table as of December 1, 2018, and that the composition does not gel after 24 hours at room temperature. Without being bound by theory, transition metals are thought to be able to catalyze the reaction of starting materials (B) and (C) at undesirably low temperatures (e.g., <65 °C).

[0058] The compositions described herein may be free of Lewis bases. "Free of Lewis bases" means that the composition contains no, or only an insufficient amount of, a compound or ionic species that can donate an electron pair to the (A) phosphonium catalyst, and that the composition does not cure sufficiently to form a gel within 20 minutes when heated at 65 °C. For example, the composition may be free of Lewis bases selected from the group consisting of the following bases: PR 10 3, P(NR 10 2)3, NR 10 3, N(SiR 10 3) x R 10 3-x 、R 10 C(NR 10 )N, P(N - R 10 )R 10 3, guanidine (C(=NR 10 )(NR 10 2)2), amidine (R 10 C(=NR 10 )NR 10 2), phosphazene, and

[0059]

Chemical formula

[0060] Method The above composition can be a one - component composition. The one - component composition contains the starting materials (A), (B), and (C) in the same part. The composition can be prepared by a method comprising the step of combining starting materials including: i) (A) a phosphonium catalyst, (B) a polyorganohydrogensiloxane, and (C) a hydrocarbonoxy - functionalized organosilicon compound, and, if present, (D) a solvent, and / or the above - mentioned optional additional components, thereby forming a mixture. The use of the starting material (D) solvent can facilitate the combination with the starting materials (A), (B), and (C). For example, one or more of the starting materials (A), (B), and (C) can be dissolved in the solvent before being mixed with the other starting materials. Alternatively, the starting materials can consist essentially of the above - mentioned starting materials (A), (B), and (C) (and optionally D). Alternatively, the starting materials can consist of the above - mentioned starting materials (A), (B), and (C) (and optionally (D)).

[0061] Mixing the starting materials to form a mixture and preparing a polyorganosiloxane composition involves not significantly reacting the silicon - bonded hydrogen atoms of the starting material (C) and the starting material (B) with a group of the formula OR 5 in which R 5It is carried out under the above - mentioned conditions. These conditions may include, for example, mixing by any convenient means. The mixing may be carried out using a conventional mixing device such as a stirred - batch kettle. Alternatively, when the hydrocarbon - oxy - functional organosilicon compound selected for starting material (C) and / or the polyorganohydrogensiloxane selected for starting material (B) is viscous or solid (e.g., gum or resin), the mixing under shear can be carried out, for example, using an extruder. The composition can be formed, for example, by mixing the above - mentioned starting materials (A), (B), and (C). The starting materials (A), (B), and (C) can be combined at a temperature below room temperature. Alternatively, the temperature for combining the starting materials (A), (B), and (C) (and (D) if present) can be from 5 °C to 30 °C. The starting materials (A), (B), and (C) (and (D) if present) can be combined simultaneously. Alternatively, the starting materials (A) and (B) (and (D) when present) can be combined to form a mixture, and then the mixture can be combined with starting material (C) (or its solvent solution), for example, by metering over a period of time, or by adding in one or more aliquots, with starting material (C) (and additional (D) when present).

[0062] Curing of the composition A method for curing a composition, the method comprising: 1) providing the composition as described above; and 2) heating the composition to a temperature sufficient to catalyze the reaction between the silicon - bonded hydrogen atoms in (B) polyorganohydrogensiloxane and the silicon - bonded hydrocarbon - oxy groups in (C) hydrocarbon - oxy - functional organosilicon compound. The product prepared in step 2) contains the reaction product (having siloxane bonds) of starting materials (B) and (C), and a by - product containing HR 5 wherein R 5This is as described above. For example, the temperature in step 2) can be ≧65°C. Alternatively, the temperature can be >30°C, but the reaction time may be longer at a lower temperature than at a higher temperature.

[0063] The method for curing the composition can optionally further include additional steps. For example, the reaction in step 2) is, as described above, the formula HR 5 to produce a by-product. The method can further include a step of removing the by-product of the formula HR 5 during and / or after step 2). The by-product HR 5 can be removed by any convenient means such as stripping and / or placing the reaction product under reduced pressure / vacuum. For example, the method can further include additional steps after step 1) and before step 2), and the additional steps include molding the composition or applying the composition onto a substrate.

Examples

[0064] These examples are provided to illustrate the present invention to those skilled in the art and should not be construed as limiting the scope of the present invention described in the claims. The starting materials used in these examples are listed in Table 1.

[0065]

Table 1

[0066] Reference Example 1 - General Procedure The reaction was carried out in an N2-filled glove box using a solvent dried over 4 Å molecular sieves. Except as specified in Table 1, all starting materials were obtained from commercial sources and used as received.

[0067] The catalyst stock solution was prepared as follows: [(C6F5)3PF][B(C6F5)4] (3.6 mg) was dissolved in CH2Cl2 (0.514 mL) to obtain [(C6F5)3PF][B(C6F5)4] stock solution A (7 mg / mL). 0.1 mL of [(C6F5)3PF][B(C6F5)4] stock solution A was added to another vial, and then CH2Cl2 (1.0 mL) was added to obtain [(C6F5)3PF][B(C6F5)4] stock solution B (0.7 mg / mL).

[0068] [P(C6F5)3F][F] (6.6 mg) was dissolved in CH2Cl2 (0.94 mL) to obtain [P(C6F5)3F + [F] stock solution A’ (7 mg / mL). 0.1 mL of [P(C6F5)3F][F] stock solution A’ was added to another vial, and then CH2Cl2 (1.0 mL) was added to obtain [P(C6F5)3F][F] stock solution B’ (0.7 mg / mL).

[0069] [(C6F5)3PF][B(C6F5)4] + NEt3 stock solution A: Et3N was added to the catalyst 1 in a molar ratio of 1:1. The Et3N stock solution (79.3 μL of Et3N in 1 mL of CH2Cl2) was first added to the reaction mixture, and then the catalyst stock solution B (0.7 mg / mL) was added.

[0070] FAB (2.9 mg) was dissolved in CH2Cl2 (0.414 mL) to obtain FAB stock solution A” (7 mg / mL). 0.1 mL of FAB stock solution A” was added to another vial, and then CH2Cl2 (1.0 mL) was added to obtain FAB stock solution B” (0.7 mg / mL).

[0071] Reference Example 2 - Setup and progress of the example reaction using catalyst 1 at room temperature. In a 30 mL vial, a magnetic stir bar, M H D 16.55 M H(0.5 mL, 0.47 g, 0.34 mmol), n-octyl Si(OMe)3 (58.8 μL, 0.054 g, 0.23 mmol), and then 67.2 μL of [(C6F5)3PF][B(C6F5)4] stock solution B (0.047 mg, M H D 16.55 M H based on 100 ppm) was added. The reaction mixture was stirred at room temperature. The reaction mixture either gelled or no change was observed. Gel formation indicates curing (crosslinking), while no change in viscosity indicates no reaction. The results are shown in Table 2 below.

[0072] Reference Example 3 - Setup and progress of the comparative example reaction 67.2 μL of FAB stock solution B (0.047 mg of FAB, M H D 16.55 M H based on 100 ppm) was used, and Reference Example 2 was repeated. The results are shown in Table 2 below.

[0073] Reference Example 4 67.2 μL of [P(C6F5)3F][F] stock solution B (0.047 mg of [P(C6F5)3F][F], M H D 16.55 M H based on 100 ppm) was used, and Reference Example 2 was repeated. The results are shown in Table 2 below.

[0074] Reference Example 5 67.2 μL of [P(C6F5)3F] stock solution B (0.047 mg of [P(C6F5)3F], M H D 16.55 M H based on 100 ppm) + 67.2 μL of NEt3 stock solution B (molar ratio 1:1 with Catalyst 1) was used, and Reference Example 2 was repeated. The results are shown in Table 2 below.

[0075] Reference Example 6 - Setup and progress of the example reaction using Catalyst 1 at 65 °C. In a 30 mL vial, a magnetic stir bar, MH D 16.55 M H (0.5 mL, 0.47 g, 0.34 mmol), n-octyl Si(OMe)3 (58.8 μL, 0.054 g, 0.23 mmol), and then 67.2 μL of [(C6F5)3PF][B(C6F5)4] stock solution B (0.047 mg, M H D 16.55 M H based on 100 ppm) was added. Then, the solution was stirred at 65 °C via a preheated aluminum block. The reaction mixture either gelled or no change was observed. Gel formation indicates curing (crosslinking), while no change in viscosity indicates no reaction. The results are shown in Table 2 below.

[0076] Reference Example 7 - Setup and Progression of Comparative Example Reactions Reference Example 6 was repeated except that 67.2 μL of [(C6F5)3PF][B(C6F5)4] (0.047 mg of [(C6F5)3PF][B(C6F5)4]) + 67.2 μL of NEt3 stock solution B (molar ratio 1:1 with Catalyst 1) was used. The results are shown in Table 2 below.

[0077] Reference Example 8 Reference Example 6 was repeated except that 67.2 μL of [(C6F5)3PF][F] stock solution A (0.047 mg of [(C6F5)3PF][F]) was used. The results are shown in Table 2 below.

[0078] [Table 2]

[0079] The data in Table 2 for Reference Examples 2 and 6 show that a one-component composition containing a phosphonium catalyst comprising a tetravalent monocation of phosphorus and a non-coordinating anion is stable (does not gel) at room temperature for 7 days, but cures in 15 minutes at a high temperature of 65°C. Reference Examples 5 and 7 showed that the presence of a Lewis base (triethylamine) hinders curing under the tested conditions. Reference Example 8 (the bottom row of Table 2) shows that Catalyst 2 containing a strongly coordinating anion did not cure the composition when tested at 65°C. Reference Example 3 shows rapid curing at room temperature when using FAB instead of the catalysts described herein.

Industrial Applicability

[0080] The above compositions are storage stable, which means that the composition does not gel at room temperature for 1 hour or less, or 5 hours or less, or 24 hours or less, or 48 hours or less, or 36 hours or less. The compositions and methods described herein are useful for preparing and curing polyorganosiloxane compositions that cure to form products such as coatings, adhesives, elastomers, and foams. The inventors have surprisingly found that the catalysts described herein cure polyorganosiloxane compositions. Furthermore, the inventors have surprisingly found that no Lewis base and / or crosslinking molecule is required to stabilize the catalysts described herein. In contrast, the presence of a Lewis base such as triethylamine can render the compositions of the present invention uncureable under the conditions tested in the above examples. The compositions and methods of the present invention provide polyorganosiloxane compositions that are storage stable at room temperature and curable by heating to a moderate temperature.

[0081] Definition and Use of Terms The abbreviations used herein have the definitions in Table 3 below.

[0082]

Table 3

[0083] All amounts, ratios, and percentages are by weight unless otherwise indicated. The amounts of all starting materials in the composition total 100 weight %. The "Summary of the Invention" and "Abstract" are incorporated herein by reference. The articles "a," "an," and "the" each refer to one or more unless otherwise specifically indicated by the context of the specification. The singular form includes the plural unless otherwise stated.

[0084] The terms "comprising" and its derivatives, e.g., "comprise" and "comprises," are meant to have the meaning of "including," "include," "consist(ing) essentially of," and "consist(ing) of," and are used herein in their broadest sense to mean including. The use of "for example," "e.g.," "such as," and "including" for listing examples is not limited to only the examples listed. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to" and includes other similar or equivalent examples.

[0085] Generally, as used herein, a hyphen "-" or a tilde "~" in a range of values means "to" or "through," ">" means "above" or "greater-than," "≧" means "at least" or "greater-than or equal to," "<" means "below" or "less-than," and "≦" means "at most" or "less-than or equal to."

[0086] Embodiments of the present invention In the first embodiment, the composition is as follows: (A) A phosphonium catalyst, which is 1 ppm to 1,000 weight ppm based on the total weight of starting materials (A) and (B), and is as follows: (i) A tetravalent monocation of phosphorus of the formula [PR 1 3R 2 + wherein each R 1 is an independently selected aryl halide group of the formula

[0087]

Chemical formula

[0088] In a second embodiment, in the composition of the first embodiment, (A) the phosphonium catalyst has the formula [(C6F5)3PF] + [B(C6F5)4] - .

[0089] In a third embodiment, in the first embodiment or the second embodiment, the polydiorganohydrogensiloxane is (i) α,ω-dimethylhydrogen siloxy terminated poly(dimethylsiloxane / methylhydrogen siloxane), (ii) α,ω-dimethylhydrogen siloxy terminated polymethylhydrogen siloxane, (iii) α,ω-trimethylsiloxy terminated poly(dimethylsiloxane / methylhydrogen siloxane), (iv) α,ω-trimethylsiloxy terminated polymethylhydrogen siloxane, and (v) α-dimethylhydrogen siloxy, ω-trimethylsiloxy terminated poly(dimethylsiloxane / methylhydrogen siloxane), (vi) α-dimethylhydrogen siloxy, ω-trimethylsiloxy terminated polymethylhydrogen siloxane, (vii) combinations of two or more of these.

[0090] In the fourth embodiment, in any one of the compositions of the first to third embodiments, (C) the hydrocarbonoxysilane is selected from the group consisting of trimethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triethylmethoxysilane, vinyldimethylethoxysilane, allyldimethylmethoxysilane, vinyldimethylmethoxysilane, dimethylphenylmethoxysilane, methyldiphenylmethoxysilane, triphenylmethoxysilane, diisobutyldiethoxysilane, n-octadecylmethyldiethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, di(4-tolyl)dimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, allyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, p-tolyltrimethoxysilane, p-tolyltriethoxysilane, pentafluorophenyltriethoxysilane, 4-trifluoromethyltetrafluorophenyltriethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltrimethoxysilane, benzyltriethoxysilane, tetraethoxysilane, and tetra-n-propoxysilane, and combinations of two or more thereof.

[0091] In the fifth embodiment, in any one of the compositions of the first to fourth embodiments, the composition further contains 1% to 99% by weight of (D) a solvent based on the total weight of the composition.

[0092] In the sixth embodiment, any one of the compositions of the first to fifth embodiments is used to prepare a product selected from the group consisting of coatings, adhesives, elastomers, and foams.

[0093] In the seventh embodiment, any one of the compositions of the first to fifth embodiments is a curable system, and the method includes: i) adding the composition to a polyorganosiloxane formulation; and ii) curing the polyorganosiloxane formulation to form a product selected from the group consisting of coatings, adhesives, elastomers, and foams.

Claims

1. (A) A phosphonium catalyst comprising (i) a tetravalent monocation of phosphorus and (ii) a non-coordinating anion, (B) a polyorganohydrogensiloxane, and (C) a hydrocarbon A composition comprising a mixture with an oxyfunctional organosilicon compound, wherein the composition does not contain a Lewis base.

2. (i) The tetravalent monocation of phosphorus is a Lewis acidic phosphorus cation of the formula [PR １ ３ R ２ , wherein each R ＋ is independently selected from the group consisting of X', -CX' ２ , and -OR ３ , each X' is independently selected from the group consisting of Br, Cl, and F, R ９ is an alkyl group or an aryl group, and each R ９ is a halogenated aryl group independently selected, the composition according to claim 1.​​

3. R １ However, the formula is: 【Chemistry 1】 It has, in the formula, each R ８ However, independently, H, X, and formula -CX ３ Selected from the bases, where each X is independently selected from Br, Cl, or F, except R ８ The composition according to claim 2, wherein at least one of is not H.

4. Each R ８ However, independently, H, Cl, F, and formula -CF ３ The composition according to claim 3, selected from the group consisting of the following groups.

5. (i) The tetravalent monocation of phosphorus is, 【Chemistry 2】 The composition according to claim 1, having the following characteristics.

6. (b) The anion is of formula [BR ３ ４ ] － It has, in the formula, each R ３ The composition according to claim 1, wherein the group is independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups.

7. (b) The anion is of formula B(C ６ F ５ ) ４ － The composition according to claim 1, having the following characteristics.

8. (B) The polyorganohydrogensiloxane is HR ４ ２ SiO １／２ , R ４ ３ SiO １／２ , HR ４ SiO ２／２ , R ４ ２ SiO ２／２ , R ４ SiO ３／２ , HSiO ３／２ , and SiO ４／２ The formula contains two or more siloxane units selected from the units, where each R ４ The composition according to claim 1, wherein the monovalent hydrocarbon group is independently selected and does not contain aliphatic unsaturated material.

9. (B) The polyorganohydrogensiloxane is as follows: (B-1) A linear polyorganohydrogensiloxane, with unit formula (HR ４ ２ SiO １／２ ) ｇ (R ４ ３ SiO １／２ ) ｈ (R ４ ２ SiO ２／２ ) ｉ (HR ４ SiO ２ ／２ ) ｊ Includes, in the formula, R ４ However, as stated above, the subscripts g, h, i, and j have values ​​such that g≧0, h≧0, quantity(g+h)=2, i≧0, j≧0, and quantity(g+j)≧1, and the quantity(i+j) is between 0 and 1,000, a linear polyorganohydrogensiloxane. (B-2) A cyclic polyorganohydrogensiloxane, with unit formula (R ４ ２ SiO ２／２ ) ｕ (R ４ HSiO ２／２ ) ｖ Includes, in the formula, R ４ However, as stated above, the subscript u is 0 or greater, the subscript v is 1 or greater, the quantity (u + v) is 3 to 15, and each R ４ However, a cyclic polyorganohydrogensiloxane is a monovalent hydrocarbon group that is independently selected, and (B-3) The combination of both (B-1) and (B-2), A composition according to claim 1, selected from the group consisting of the following.

10. (C) The hydrocarbon oxy-functional organosilicon compound is of formula -OR ５ Each molecule has at least one silicon bonding group on average, and in the formula, each R ５ The composition according to claim 1, wherein the monovalent hydrocarbon group is independently selected from carbon atoms 1 to 6.

11. (C) The hydrocarbon oxy-functional organosilicon compound is as follows: (C-1) Hydrocarbon oxysilane, formula: R ７ （４－ｂ） Si ( OR ５ ) ｂ The formula includes, and in the formula, each R ７ However, independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, each R ５ However, it is a monovalent hydrocarbon group with 1 to 6 carbon atoms, and the subscript b is 1 to 4, which is a hydrocarbon oxysilane. (C-2) Hydrocarbon oxy-functional organosiloxane oligomer or polymer, wherein formula: 【Transformation 3】 The formula has such that each D independently represents an oxygen atom, a divalent hydrocarbon group, a divalent siloxane group, or a combination of a divalent hydrocarbon group and a divalent siloxane group, and each R Ｘ However, independently, formula - OR ５ It represents the basis of, and in the formula, each R ５ However, as stated above, each R ６ However, R ５ The above-mentioned group consists of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, where the subscript c represents 0, 1, 2, or 3, the subscript e represents 0, 1, or 2, and the subscript d has a value of 0 or greater, provided that in the formula there is at least one R on average. Ｘ The composition according to claim 1, having a formula selected from the group consisting of a hydrocarbon oxy-functional organosiloxane oligomer or polymer, where the sum of (e + c) is at least 1, and a combination of (C-3)(C-1) and (C-2).

12. (C-1) The hydrocarbon oxysilane is present, and the hydrocarbon oxysilane is of formula: R ７ SiOR ５ ３ It has, in the formula, R ７ However, each R is an alkyl group consisting of 1 to 20 carbon atoms. ５ The composition according to claim 11, wherein the alkyl group has 1 to 4 carbon atoms.

13. (D) The composition according to claim 1, further comprising a solvent.

14. The composition according to claim 1, wherein the composition does not contain a transition metal.

15. It is a method, 1) A step of providing the composition according to any one of claims 1 to 14, 2) The step of heating the composition to a temperature sufficient to catalyze the reaction between (B) the silicon-bonded hydrogen atoms in the polyorganohydrogensiloxane and (C) the silicon-bonded hydrocarbon oxy groups in the hydrocarbon oxy-functional organosilicon compound, The method may optionally include an additional step after step 1) and before step 2), wherein the additional step further includes a step of molding the composition or applying the composition onto a substrate.

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