Compositions and Methods for Silyl Hydride Reactions Catalyzed by Fluorinated Aryl Borane Lewis Acids

Abstract

The composition includes a silyl hydride (having at least one silicon-bonded hydrogen atom per molecule) and a fluorinated triarylborane Lewis acid. In the method, the Lewis acid catalyzes the reaction of the silicon-bonded hydrogen atom from the silyl hydride with water, thereby forming a siloxane bond in the resulting product. The composition and method can be used to form siloxane intermediates and cured networks.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 043,149, filed on June 24, 2020, under 35 U.S.C. § 119(e). U.S. Provisional Patent Application No. 63 / 043,149 is incorporated herein by reference.

[0002] (Field of the Invention) The composition includes a silyl hydride (having at least one silicon - bonded hydrogen atom per molecule) and a fluorinated triarylborane Lewis acid. In the method, the Lewis acid catalyzes the reaction of the silicon - bonded hydrogen atom from the silyl hydride with water, thereby forming a siloxane bond in the resulting product. The composition and method can be used to form siloxane intermediates and cured networks.

Background Art

[0003] The catalysts mainly used in the preparation of both siloxane intermediates and siloxane cured networks from Si - H functional silanes and siloxanes are platinum - based catalysts. Due to the increasingly high cost of platinum (Pt) and other drawbacks such as yellowing of the cured siloxane composition or the formation of black precipitates over time, alternative methods to Pt - based catalysts are needed in the industry. Further, although Pt - based catalysts are effective, they can also suffer from the drawback that they require high temperatures (80 °C - 110 °C) to achieve sufficient reactivity to catalyze the formation of siloxane bonds.

Summary of the Invention

[0004] The composition includes A) a fluorinated triarylborane Lewis acid and B) a silyl hydride. The composition may be used in a method that includes combining A) a fluorinated triarylborane Lewis acid, B) a silyl hydride, and C) water, thereby forming a product. The product has a siloxane bond formed by the reaction of the SiH moiety from the silyl hydride with water.

BEST MODE FOR CARRYING OUT THE INVENTION

[0005] This composition contains A) a fluorinated triarylborane Lewis acid and B) a silyl hydride. The composition may not contain water. Alternatively, the composition may consist essentially of A) a fluorinated triarylborane Lewis acid and B) a silyl hydride. Alternatively, the composition may consist of A) a fluorinated triarylborane Lewis acid and B) a silyl hydride. The composition may be stored, prior to use, under conditions that prevent the reaction of silicon-bonded hydrogen atoms from the silyl hydride, for example, under anhydrous conditions.

[0006] The method described herein includes the step of combining 1) starting materials comprising (or consisting essentially of, or consisting of) A) and B) as described above with C) water. The combining step is carried out under conditions that react the silicon-bonded hydrogen atoms of starting material B) to form a by-product containing a siloxane bond and hydrogen.

[0007] 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. The mixing may be carried out at any convenient temperature, for example, room temperature. Alternatively, when the silyl hydride selected for starting material B) is viscous, the mixing under shear can be carried out using, for example, an extruder. The composition can be formed, for example, by mixing starting materials A) and B) described above. Starting materials A) and B) can be heated during mixing at a temperature of 50°C to 150°C, or 100°C to 125°C. Optionally, a solvent which is starting material D) can be used to facilitate the combination of starting materials A) and B). For example, starting material A) may be dissolved in the solvent before mixing with starting material D). Without wishing to be bound by theory, by using the fluorinated triarylborane Lewis acid described herein instead of a Pt-based catalyst or other catalyst such as FAB, when starting materials A) and B) are present together before step 1) of the method described herein, it is believed that the advantages of the stability of the composition can be provided even when starting materials A) and B) are combined while being heated.

[0008] In step 1) of the present method, when a composition containing starting materials A) and B) is exposed to C) water, the reaction between the silicon-bonded hydrogen atoms and water starts, and siloxane bonds are formed. Water may be mixed with starting materials A) and B) using the means described above, and starting materials A), B), and C) may be combined simultaneously in step 1). Alternatively, the composition containing starting materials A) and B) may be prepared before step 1), and then, in step 1), the composition may be exposed to water, for example, by exposure to humid air. The exposure to water may be carried out at 5°C to 150°C, or at room temperature to 150°C, or at 5°C to 125°C, or at room temperature to 125°C. Although not wishing to be bound by theory, the temperature for the exposure to water is thought to depend on the silyl hydride selected. For example, when starting material B) contains, for example, a silyl-functionalized polyolefin, a higher temperature (for example, 50°C to 150°C) may be used. When starting material B) is, for example, a silane, a lower temperature may be sufficient. For example, the temperature may alternatively be room temperature to 70°C, 5°C to 70°C, or 5°C to 65°C, or 10°C to 60°C, or 15°C to 50°C, or 20°C to 35°C, or 5°C to 30°C, or 30°C.

[0009] The method may optionally further include one or more additional steps. The method may further include step 2) a step of removing H2 generated during and / or after step 1) during the formation of the product, and / or step 3) a step of removing and / or neutralizing the residual fluorinated triarylborane Lewis acid in the product. The by-product H2 can be removed by any convenient means, such as stripping and / or combustion. The step of removing and / or neutralizing may be carried out by adding E) a neutralizing agent to the product, or alternatively, by adding E) a neutralizing agent to the product and then optionally filtering the product. Steps 2) and 3) may be carried out in any order. For example, if particulate by-products are present as a result of neutralization, the method may further include step 4) a step of removing fine particles such as alumina by any convenient means, such as filtration, after neutralization.

[0010] Starting material A) Catalyst The starting material A) in the compositions and methods described herein is a fluorinated triarylborane Lewis acid. The fluorinated triarylborane Lewis acid has the formula:

[0011] [Chemical formula] having, wherein each R o is an ortho substituent, each R m is a meta substituent, each R p is a para substituent, R 2 is optional and contains a functional group or a functional polymer group, and the subscript x is 0 or 1. In the above formula, each of R o1-6 , each of R m1-6 , and each of R p1-3 is independently selected from H, F, or CF3, provided that not all of R o1-6 , R m1-6 , and R p1-3 can be F simultaneously, and not all of R o1-6 , R m1-6 , and R p1-3 can be H simultaneously. When two or more of R o1-4 are CF3, R o5 and R o6 are each independently selected from H or F. R 2 is optional, i.e., R 2 exists when the subscript x = 1, and R 2 does not exist when the subscript x = 0. R 2 may be a Lewis base that forms a complex with the fluorinated triarylborane Lewis acid and / or a molecule or moiety containing at least one electron pair available for forming a coordination bond with the Lewis acid, as described for R 4 in paragraphs

[0024] -

[0025] of WO 2019 / 055740. Examples of R 2 include cyclic ethers such as tetrahydrofuran or tetrahydropyran. Alternatively, R 2may be tetrahydrofuran (THF).

[0012] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , and R o6 may each be H. Alternatively, R o1 , R o2 , R o3 , and R o4 may each be H. Alternatively, R o5 and R o6 may each be F.

[0013] Alternatively, R m1 , R m2 , R m3 , R m4 , R m5 , and R m6 may each be CF3. Alternatively, R m1 , R m2 , R m3 , and R m4 may each be CF3. Alternatively, R m5 and R m6 may each be F. Alternatively, R m5 and R m6 may each be H.

[0014] Alternatively, R p1 , R p2 , and R p3 may each be H. Alternatively, R p1 and R p2 may be H. Alternatively, R p3 may be F. Alternatively, R p3 may be CF3.

[0015] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R o6 , Rp1 、R p2 、and R p3 each may be H, R m1 、R m2 、R m3 、R m4 、R m5 、and R m6 each may be CF3. The subscript x may be 1. Alternatively, starting material A) may include tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct.

[0016] Alternatively, R o1 、R o2 、R o3 、R o4 、R o5 、R o6 、R m5 、R m6 、R p1 、and R p2 each may be H, R m1 、R m2 、R m3 、R m4 、and R p3 each may be CF3. The subscript x may be 1. Alternatively, starting material A) may include bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct.

[0017] Alternatively, R o1 、R o2 、R o3 、R o4 、R m5 、R m6 、R p1 、and R p2 each may be H, R o5 、R o6 、and R p3 each may be F, R m1 、R m2 、R m3 、R m4Each of them may be CF3. The subscript x may be 1. Alternatively, starting material A) may contain bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct.

[0018] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 , R p2 , and R p3 each may be H, R o5 and R o6 may be F, R m1 , R m2 , R m3 , and R m4 each may be CF3. The subscript x may be 1. Alternatively, starting material A) may contain bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct.

[0019] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R m6 , R p1 , R p2 , and R p3 each may be H, R m1 , R m2 , R m3 , R m4 , R m5 , and R o6 each may be CF3. The subscript x may be 0. Alternatively, starting material A) may contain bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane.

[0020] Alternatively, R m1 , R p1 , R o2 , R o3 , Ro4 , R p2 , R p3 , R o5 , and R m6 may each be H, R o1 , R m2 , R m3 , R m4 , R o6 , and R m5 may each be CF3. Subscript x may be 0. Alternatively, starting material A) may contain (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane.

[0021] Alternatively, R o1 , R o2 , R o3 , R o4 , R p1 , and R p2 may each be H, R o5 , R o6 , R m5 , and R m6 may each be F, R m1 , R m2 , R m3 , R m4 , and R p3 may each be CF3. Subscript x may be 1. Alternatively, starting material A) may contain bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct.

[0022] Alternatively, the fluorinated triarylborane Lewis acid may be selected from the group consisting of A1) tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct, A2) bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct, A3) bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct, A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct, A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane, A6) (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane, A7) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct, and combinations of two or more of A1) to A7). Alternatively, the fluorinated triarylborane Lewis acid may be selected from the group consisting of A2), A3), A4), A5), A6), A7), and combinations of two or more of A2) to A7). Alternatively, the fluorinated triarylborane Lewis acid may be selected from the group consisting of A4), A5), A6), and combinations of two or more of A4), A5), and A6). Alternatively, the fluorinated triarylborane Lewis acid may be selected from the group consisting of A4), A5), and A6). Alternatively, the fluorinated triarylborane Lewis acid may be selected from the group consisting of A4) and A6).

[0023] The fluorinated triarylborane Lewis acid is known in the art and can be prepared by appropriately changing the starting materials by known methods, for example, the methods disclosed in International Publication No. 2019 / 055740, particularly in paragraphs

[0052] to

[0096] .

[0024] The amount of starting material A) varies depending on the types and amounts of other starting materials used, but starting material A) may be present in an amount of 0.5 ppm to 5 mol%, or 5 ppm to 6000 ppm, based on the total weight of starting materials A) and B) in the composition. Alternatively, the amount may be, on the same basis, 5 ppm to 600 ppm, or 5 ppm to 500 ppm, or 5 ppm to 100 ppm.

[0025] B) Silyl hydride Starting material B) in the compositions and methods described herein is a silyl hydride. The term "silyl hydride" means a molecule containing at least one silicon-bonded hydrogen atom (SiH) per molecule. Alternatively, the silyl hydride may have two or more SiHs per molecule. The silyl hydride used herein can form siloxane bonds in the presence of A) fluorinated triarylborane Lewis acid and C) water. A silyl hydride containing multiple Si-H bonds may be capable of self-crosslinking in the presence of A) fluorinated triarylborane Lewis acid and C) water. Starting material B) can be selected from the group consisting of B1) silane, B2) polyorganohydrogensiloxane, B3) silyl-functionalized polyolefin, and combinations of two or more of B1), B2), and B3).

[0026] The silyl hydride can be B1) silane (e.g., having one silicon atom per molecule). Alternatively, the silyl hydride may be an oligomer or polymer. The polymeric silyl hydride can be linear, branched, or resinous. For example, the silyl hydride may be B2) polyorganohydrogensiloxane. Alternatively, the silyl hydride may be B3) an organic polymer functionalized with a SiH-containing moiety.

[0027] B1) Silane Starting material B1) is a silane of the formula H k SiR 5 (4-k) wherein each R 5is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, and the subscript k is 1 to 3, or 1 or 2, or 1. R 5 Examples of suitable monovalent hydrocarbon groups for R include, but are not limited to, alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and its branched isomers), cycloalkyl such as cyclopentyl and cyclohexyl, alkenyl such as vinyl, allyl, butenyl, and hexenyl, and aryl such as phenyl, tolyl, xylyl, naphthyl, benzyl, 1-phenylethyl, and 2-phenylethyl. R 5 Examples of the monovalent halogenated hydrocarbon groups for R include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl groups, fluorinated alkyl groups such as fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 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. Alternatively, each R 5 may be a monovalent hydrocarbon group, or an alkyl group, or an aryl group. Alternatively, each R 5 may be an alkyl group, such as an alkyl group having 1 to 6 carbon atoms. Alternatively, each R 5 may be methyl or ethyl. Alternatively, the starting material B1) may be a silane of the formula HSiR 5 3, wherein each R 5 is an alkyl group having 1 to 6 carbon atoms.

[0028] Examples of suitable silanes for the starting material (B1) are known in the art and are commercially available. Suitable silanes include triethylsilane, dimethylethylsilane, diethylmethylsilane, dimethylisopropylsilane, dimethyl-tert-butylsilane, triisopropylsilane, chloromethyldimethylsilane, tripropylsilane, tributylsilane, triisobutylsilane, trihexylsilane, trioctylsilane, cyclohexyldimethylsilane, dimethylphenylsilane, diphenylmethylsilane, triphenylsilane, phenylsilane, bromoundecylsilane, 2-chloroethylsilane, dodecylsilane, n-octadecylsilane, and (tridecafluoro-1,1,2,2-tetrahydrooctyl)silane, which are available from Sigma-Aldrich Inc., St. Louis, Missouri, USA or Gelest Inc., Morrisville, Pennsylvania, USA.

[0029] B2) Polyorganohydrogensiloxane When using the polyorganohydrogensiloxane as the starting material B2), the polyorganohydrogensiloxane may be a homopolymer or a copolymer. The polyorganohydrogensiloxane may be linear, branched, or resinous. The silicon-bonded hydrogen atoms in the polyorganohydrogensiloxane can be located at the terminal, pendant, or both terminal and pendant positions.

[0030] The polyorganohydrogensiloxane is HR 4 2SiO 1 / 2 、R 4 3SiO 1 / 2 、HR 4 SiO 2 / 2 、R 4 2SiO 2 / 2 、R 4 SiO 3 / 2 、HSiO 3 / 2 、and SiO 4 / 2 It may contain two or more siloxane units selected from the units. In the above formulas, each R 4is a monovalent hydrocarbon group independently selected and containing no aliphatic unsaturation. R 4 Examples of suitable monovalent hydrocarbon groups for 4 include alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and its branched isomers), cycloalkyl such as cyclopentyl and cyclohexyl, and aryl such as phenyl, tolyl, xylyl, naphthyl, benzyl, 1-phenylethyl, and 2-phenylethyl, but are not limited thereto. Alternatively, each R 4 may be an alkyl group or a cycloalkyl group. Alternatively, each R 4 may be an alkyl group such as methyl.

[0031] When the polyorganohydrogensiloxane is linear, i.e., when it is a polydiorganohydrogensiloxane, the polydiorganohydrogensiloxane may have the unit formula (HR 4 2SiO 1 / 2 ) g (R 4 3SiO 1 / 2 ) h (R 4 2SiO 2 / 2 ) i (HR 4 SiO 2 / 2 ) j , where R 4 is as described above, and the subscripts g, h, i, and j have values such that g≥0, h≥0, the average value of the quantity (g + h) is 2, i≥0, j≥0, the quantity (g + j)≥1, and the quantity (i + j) is in the range of 0 to 1000.

[0032] Alternatively, the polydiorganohydrogensiloxane may have the formula

[0033]

Chemical formula

[0034] Suitable polyorganohydrogensiloxanes are i) pentamethyldisiloxane, ii) bis(trimethylsiloxy)methyl-silane, iii) tetramethyldisiloxane, iv) bis-dimethylhydrogensiloxy-terminated polydimethylsiloxane, v) bis-dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), vi) bis-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, vii) bis-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), viii) bis-trimethylsiloxy-terminated polymethylhydrogensiloxane, ix) H(CH3)2SiO 1 / 2 units and SiO 4 / 2 resins consisting essentially of units, and exemplified by combinations of two or more of i) to ix).

[0035] Methods for preparing linear and branched polyorganohydrogensiloxanes suitable for use as starting material B2), such as hydrolysis and condensation of organohalosilanes, are well known in the art, as exemplified in U.S. Patent Nos. 5,310,843, 4,370,358, 4,707,531, and 4,329,273. Polyorganohydrogensiloxanes are also commercially available, such as those available from Gelest under the trade names DMS-HM15, DMS-H03, DMS-H25, DMS-H31, and DMS-H41.

[0036] B3) Silyl-functionalized polyolefin Starting material B3) is a polyolefin having a silicon-bonded hydrogen functional group of formula (B3-1):

[0037]

Chemical formula

[0038] The starting material B3) silyl-functionalized polyolefin may have a silyl group of formula (B3-1) at a pendant position. For example, a silyl-functionalized polyolefin having a pendant silyl group has a unit formula (B3-2):

[0039] [Chemical formula] It may be a SiH-functional polyolefin copolymer containing, wherein R 1 and the subscript a are as described above.

[0040] Each D in the unit formula (B3-2) 1 is independently a divalent hydrocarbon group having 2 to 50 carbon atoms. Suitable divalent hydrocarbon groups for D 1 include alkylene groups such as ethylene, propylene, butylene, hexylene, or octylene, arylene groups such as phenylene, or

[0041] [Chemical formula] alkylarylene groups such as etc. are exemplified. Alternatively, each D 1 is an alkylene group such as ethylene, propylene, or octylene.

[0042] In the unit formula (B3-2), each R 25 is independently H, a monovalent hydrocarbon group having 1 to 18 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 18 carbon atoms. Suitable monovalent hydrocarbon groups for R 25 have 1 to 18 carbon atoms and are R 1is exemplified by what is described in this specification. Suitable monovalent halogenated hydrocarbon groups include haloalkyl groups, halogenated carbocyclic groups, and haloalkenyl groups. Examples of haloalkyl groups include trifluoromethyl (CF3), fluoromethyl, trifluoroethyl, 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, 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, as well as chlorinated alkyl groups such as chloromethyl, 3-chloropropyl, 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl, and other fluorinated alkyl groups. Examples of haloalkenyl groups include chloroallyl groups. Alternatively, each R 25 can be H or an alkyl group having 1 to 6 carbon atoms. Alternatively, each R 25 can be H.

[0043] In the unit formula (B3-2), the subscript M is at least 1. The subscript N is at least 1. Alternatively, 1 ≦ M ≦ 10. Alternatively, 10 ≦ N ≦ 20,000. Alternatively, the subscripts M and N may have values such that the quantity M / (M + N) is 0.01 mol% ≦ M / (M + N) ≦ 10 mol%. Alternatively, the subscripts M and N may have values sufficient to give the copolymer an Mn of 1,000 to 500,000.

[0044] This SiH-functional polyolefin may further contain end-capping groups of R 21 at each end. Each R 21may independently be a saturated monovalent hydrocarbon group such as an alkyl group (e.g., methyl), or an unsaturated monovalent hydrocarbon group having one or more double bonds (e.g., a monovalent hydrocarbon group containing a vinyl functional group, a vinylene functional group, or a vinylidene functional group). Examples of such SiH-functional polyolefins (silyl-functional olefin interpolymers) and methods for their preparation are disclosed, for example, in U.S. Patent No. 6,624,254 to Arriola et al.

[0045] Alternatively, B3) the silyl-functional polyolefin may include a silyl-terminated polyolefin having 1 to 2 terminal silyl groups of formula (B3-1) per molecule. The silyl-terminated polyolefin has a unit formula (B3-3):

[0046] [Chemical formula] and may have, wherein the subscript a and R 1 are as described above, the subscript f is 0 to 1, the subscripts t and u have relative values such that 0 < t ≤ 1, 0 ≤ u ≤ 1, the subscript g is 1 or more, each R et represents an ethylene unit, and each R O represents an olefin unit other than ethylene. R O may be an α-olefin or a cyclic olefin. Examples of α-olefins are as follows and include ethylene, propylene, and octene. Examples of cyclic olefins are as follows and include ethylidene norbornene, norbornene, vinyl norbornene, vinyl cyclohexene, cyclohexene, and cyclopentene. Alternatively, the subscript g may be 1 to 500, or 10 to 400, or 18 to 360. Alternatively, the subscript g may have a value sufficient to give the silyl-terminated polyolefin an Mn of 500 to 50,000 g / mol, or 500 to 10,000 g / mol.

[0047] Alternatively, the silyl-terminated polyolefin has a unit formula (B3-4):

[0048] [Chemical formula] may have, wherein the subscripts a, f, g, t, and u, and R 1 are as described above. Each R 7 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. The monovalent hydrocarbon group of R 7 is alkyl, alkenyl, or aryl, or alkyl. Alternatively, R 7 may be an alkyl group having 2 to 12 carbon atoms, or 2 to 6 carbon atoms. Alternatively, each R 7 is a hexyl group.

[0049] The silyl-terminated polyolefin may have one terminal silyl group per molecule (i.e., subscript f = 1). Examples of this silyl-terminated polyolefin having a silyl group at one end of the polymer chain include dimethyl, hydrogen silyl-terminated polyethylene, dimethylhydrogen silyl-terminated poly(ethylene / octene) copolymer, methyldihydrogen silyl-terminated polyethylene, methyldihydrogen silyl-terminated poly(ethylene / octene) copolymer, diphenylhydrogen silyl-terminated polyethylene, diphenylhydrogen silyl-terminated poly(ethylene / octene) copolymer, phenyldihydrogen silyl-terminated polyethylene, phenyldihydrogen silyl-terminated poly(ethylene / octene) copolymer, chlorophenylhydrogen silyl-terminated polyethylene, or chlorophenylhydrogen silyl-terminated poly(ethylene / octene) copolymer. This silyl-terminated polyolefin can be prepared by the processes described in International Publication No. 2019 / 082992 corresponding to U.S. Patent Application No. 62 / 644635 filed on March 19, 2018, and International Publication No. 2019 / 182986 corresponding to U.S. Patent Application No. 62 / 644624 filed on March 19, 2018, both of which are incorporated herein by reference.

[0050] Alternatively, the silyl-terminated polyolefin as starting material B3) may have two silyl end groups per molecule (i.e., in formulas (B3-3) and (B3-4), the subscript f = 0, and the silyl-terminated polyolefin is telechelic). Such a telechelic silyl-terminated polyolefin may be prepared by methods such as those disclosed in International Publication No. WO 2019 / 182993 corresponding to U.S. Patent Application No. 62 / 644,808 filed on March 19, 2018, which is incorporated herein by reference.

[0051] The starting material B3) may be a single silyl hydride or may contain two or more silyl hydrides having at least one different property. For example, the starting material B3) may be a silyl-functionalized polyolefin or may contain two or more silyl-functionalized polyolefins having at least one different property among the following properties: structure, viscosity, average molecular weight, olefin block, and sequence.

[0052] (C) Water The water as starting material C) is generally not limited and may be used undiluted (i.e., without any solvent) and / or pure (i.e., free of or substantially free of minerals and / or other impurities). For example, the water (C) may be treated before use in the above-described methods or may be untreated. Examples of processes that can be used to purify water include distillation, filtration, deionization, and combinations of two or more thereof, by which deionization, distillation, and / or filtration can be performed on the water. Alternatively, the water may be untreated (e.g., tap water or well water provided by a municipal water system used without further purification).

[0053] Water can be used in any amount selected by those skilled in the art depending on various factors such as the specific catalyst selected for starting material A), the reaction parameters used, and the scale of the reaction (e.g., the total amount of starting material B) and the SiH content).

[0054] D) Solvent Starting material D) can be any solvent that can be used to facilitate the combination of starting materials. The solvents used herein help to fluidize the starting materials but do not essentially 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 materials. "Volatility" refers to the vapor pressure of the solvent. For example, the fluorinated triarylborane Lewis acid, which is starting material A), may be dissolved in a solvent before step 1). Alternatively, starting material B) may be dissolved in a solvent, for example, when starting material B) is viscous, elastomeric, or resinous. The solvent can be used in any amount selected by those skilled in the art according to various factors such as the selection of starting material B) and the solubility of starting material A) therein.

[0055] 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 may be a halogenated hydrocarbon such as dichloromethane, 1,1,1-trichloroethane, or methylene chloride. One solvent, or a combination containing two or more solvents, may be used herein.

[0056] The amount of the solvent may vary depending on various factors such as the type of solvent selected, and the amount and type of other starting materials selected. However, the amount of the solvent may be in the range of 0.1% to 99%, or 2% to 50%, based on the total weight of starting materials A) and B).

[0057] Starting material E) Neutralizing agent The starting material E) is a neutralizing agent and may optionally be used after the product is formed to neutralize the starting material A). Alumina, triphenylamine, triethylamine, triphenylphosphine, and phenylacetylene are suitable neutralizing agents. Neutralizing agents are known in the art and are commercially available, for example, from Millipore Sigma, St. Louis, Missouri, USA. The amount of the neutralizing agent depends on various factors including the amount of the starting material A), but the starting material E) may be present in an amount sufficient to provide a weight ratio of neutralizing agent to fluorinated triarylborane Lewis acid (E:A ratio) of 100:1 to 1:1000, or 1:1 to 1000:1, or 100:1 to 1:1. Alternatively, when the neutralizing agent is triphenylphosphine or phenylacetylene, the E:A ratio may be 1:1 to 20:1. Alternatively, when the neutralizing agent is alumina, the E:A ratio may be 100:1 to 1000:1.

[0058] Method of use The compositions and methods described herein can be used in the preparation of siloxanes, siloxane organic hybrid copolymers, intermediates, and / or branched siloxane networks. Without wishing to be bound by theory, it is believed that the compositions and methods described herein can be used as curing systems for various formulations and applications. The compositions provide the advantage of storage stability when the starting materials A) and B) are combined and stored before use.

Examples

[0059] These examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention as claimed. The starting materials described in Table 1 and Reference Examples 1 and 2 were used in the examples herein.

[0060]

Table 1

[0061] Reference Example 1 - General procedure Unless otherwise specified, all experimental procedures and manipulations of chemical substances were carried out inside a nitrogen-purged glove box or on a Schlenk line. All bulk reaction solvents (toluene, diethyl ether, hexane, tetrahydrofuran (THF)) were dried by passing through columns of alumina and Q5 reactive scavenger. All other solvents were purchased from Aldrich in anhydrous grade and stored over activated 3 Å molecular sieves prior to use. NMR solvents (CDCl3, CD2Cl2, and C6D6) obtained from Cambridge Isotope Laboratories, Inc. were dried over activated 3 Å molecular sieves or, in the case of C6D6, dried using Na / K alloy. 1-Bromo-3,5-bis(trifluoromethyl)benzene, 1-bromo-2,5-bis(trifluoromethyl)benzene, 1-bromo-2,6-difluorobenzene, 1-bromo-2,4,6-trifluorobenzene, and 1-bromo-4-trifluoromethylbenzene were purchased from Oakwood Chemical. 1-Bromo-2,3,5,6-tetrafluoro-4-trifluoromethylbenzene was purchased from Alfa Aesar. FAB was purchased from TCI. All other reagents were purchased from Sigma-Aldrich and used as received. 1.00 M decanol in toluene with 1,10-phenanthroline as an indicator was used to titrate n-butyllithium (solution in hexane) prior to use. 1

[0062] Multinuclear NMR spectra ( 1 H, 13 C, 19 F, 29 Si, 11 B) were collected on one of the following Varian MR-400 or Varian VNMRS-500 instruments. 11 B NMR spectra were collected only on the Varian VNMRS-500. 1 H and 13 C NMR chemical shifts were referenced in parts per million relative to the residual solvent peak. 1In H-CD2Cl2, it is 5.32 ppm; in C6D6, it is 7.15 ppm; in CDCl3, it is 7.25 ppm. 13 In C-CD2Cl2, it is 54.00 ppm; in C6D6, it is 128.00 ppm; in CDCl3, it is 77.00 ppm. 11 11B NMR chemical shifts were externally referenced to BF3(Et2O) (0 ppm). 19 19F NMR chemical shifts were externally referenced to CFCl3 (0 ppm). Except when dry ice or ice was the only cooling means, the sub-ambient reaction temperature was measured using an Extech Instruments EasyView™ 10 Dual K model EA 10 thermometer equipped with a fine JKEM sensor PTFE wire K 36INJ.

[0063] Reference Example 2 - Synthesis Procedure - Preparation of Starting Materials The preparation of lithium (diethyl etherate)(3,5-bis(trifluoromethyl)phenyl)triisopropoxyborate was carried out as follows. __________________ 1 Watson, S.C.; Eastham, J.F. "Colored indicators for simple direct titration of magnesium and lithium reagents", J. Organomet. Chem., 1967, 9, 165 - 168.

[0064]

Chemical formula

[0065] To a cold (-78 °C, CO2(s) bath) solution of 1-bromo-3,5-bis(trifluoromethyl)benzene (18.52 g, 63.19 mmol) in diethyl ether (200 mL) was added n-butyllithium (23.0 mL, 2.61 M in hexane, 60.03 mmol) with stirring. The reaction mixture was stirred at -78 °C for 3 hours to form a precipitate. Triisopropyl borate (11.86 g, 63.06 mmol) in ether (20 mL) was added slowly. The reaction mixture was stirred at -78 °C for 1 hour, then warmed to ambient temperature and stirred for 1 hour to obtain a slightly turbid solution. The reaction mixture was filtered and the volatiles were removed under reduced pressure to give a solid. The obtained solid was triturated with hexane, filtered, and the volatiles were removed under reduced pressure to give the product as a colorless powder. Yield: 23.16 g, 94.53%. The compound was initially isolated as its ether adduct. 1 1H NMR (500 MHz, THF-d8) δ 8.15 (s, 2H), 7.57 (s, 1H), 3.79 (p, J = 6.1 Hz, 3H), 0.95 (d, J = 6.1 Hz, 18H). 13 13C NMR (126 MHz, THF-d8) δ 159.12, 134.71, 128.90 (q, J = 31.3 Hz), 125.91 (q, J = 271.8 Hz), 118.70, 67.41 (dtd, J = 44.2, 22.2, 2.9 Hz), 61.67, 26.53 (d, J = 17.7 Hz), 25.28 (dtd, J = 40.4, 20.1, 3.0 Hz). 19 19F NMR (470 MHz, THF-d8) δ -63.02. 11 11B NMR (160 MHz, THF-d8) δ 3.84.

[0066] (3,5-Bis(trifluoromethyl)phenyl)diisopropoxyborane was prepared as follows.

[0067]

Chemical formula

[0068] To a solution of lithium (diethyl etherate) (3,5-bis(trifluoromethyl)phenyl)triisopropoxyborate (8.00 g, 19.6 mmol) in diethyl ether (100 mL) was added hydrogen chloride solution (12.3 mL, 2 M in ether, 24.6 mmol), and a precipitate formed immediately. The reaction mixture was stirred for 2 hours, filtered, and the volatiles were removed under reduced pressure. The resulting residue was extracted with hexane, filtered, and the volatiles were removed under reduced pressure to afford the product as an oil. Yield: 5.10 g, 76.1%. 1 1H NMR (500 MHz, chloroform-d) δ 8.01 (d, J = 1.9 Hz, 2H), 7.89 (dt, J = 2.0, 1.0 Hz, 1H), 4.59 (hept, J = 6.1 Hz, 1H), 1.27 (d, J = 6.2 Hz, 6H). 13 13C NMR (126 MHz, chloroform-d) δ 134.19, 132.85 (td, J = 3.7, 1.9 Hz), 130.85 (q, J = 32.9 Hz), 123.67 (d, J = 272.6 Hz), 123.04 (hept, J = 3.9 Hz), 67.00, 24.58. 19 19F NMR (470 MHz, chloroform-d) δ -63.34. 11 11B NMR (160 MHz, chloroform-d) δ 26.66.

[0069] The preparation of lithium (diethyl etherate) bis(3,5-bis(trifluoromethyl)phenyl)diisopropoxyborane was carried out as follows.

[0070]

Chemical formula

[0071] A solution of 1-bromo-3,5-bis(trifluoromethyl)benzene (4.26 g, 14.5 mmol) in diethyl ether (200 mL) was cooled to -78 °C (CO2(s) bath), and n-butyllithium (5.30 mL, 2.61 M in hexane, 60.0 mmol) was added with stirring. The reaction mixture was stirred at -78 °C for 1 hour to form a precipitate. (3,5-Bis(trifluoromethyl)phenyl)diisopropoxyborane (4.82 g, 14.1 mmol) in ether (15 mL) was added slowly. The reaction mixture was stirred at -78 °C for 1 hour (some solid was visible), then warmed to ambient temperature and stirred overnight to give a clear solution. The volatiles were removed under reduced pressure to give a solid that looked like crystals. The solid was dissolved in hexane, the solution was filtered, and placed in the freezer over the weekend. A large amount of crystalline material was formed. The supernatant was decanted, and the volatiles were removed under reduced pressure to give a colorless crystalline material. Yield: 8.23 g, 93.5%. 1 1H NMR (400 MHz, chloroform-d) δ 7.99 (d, J = 1.9 Hz, 2H), 7.74 (dt, J = 1.8, 1.0 Hz, 1H), 3.81 (q, J = 7.1 Hz, 2H), 3.35 (hept, J = 6.1 Hz, 1H), 1.45 (t, J = 7.1 Hz, 3H), 0.78 (d, J = 6.1 Hz, 6H). 13 13C NMR (101 MHz, chloroform-d) δ 153.43, 134.19 - 133.42 (m), 129.51 (q, J = 31.9 Hz), 124.42 (q, J = 272.4 Hz), 119.68 (hept, J = 4.0 Hz), 66.83, 63.03, 25.48, 14.66. 19 19F NMR (376 MHz, chloroform-d) δ -63.05. 11 11B NMR (160 MHz, chloroform-d) δ 5.12.

[0072] The preparation of bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane was carried out as follows.

[0073]

Chemical formula

[0074] To a solution of lithium(diethyl etherate)bis(3,5-bis(trifluoromethyl)phenyl)diisopropoxyborate (5.00 g, 7.86 mmol) in diethyl ether (100 mL) was added a hydrogen chloride solution (5.5 mL, 2 M in ether, 11 mmol), and a precipitate immediately formed. The reaction mixture was stirred for 1 h and the volatiles were removed under reduced pressure. The residue was extracted with hexane, filtered, and the volatiles were removed under reduced pressure to give the product as a colorless powder. Yield: 3.98 g, 102% (some residual solvent present). 1 H NMR (400 MHz, chloroform-d) δ 8.00 (ddd, J = 2.2, 1.4, 0.7 Hz, 2H), 7.98 (dq, J = 1.9, 0.6 Hz, 4H), 4.54 (hept, J = 6.1 Hz, 1H), 1.37 (d, J = 6.1 Hz, 6H). 13 C NMR (101 MHz, chloroform-d) δ 138.42, 133.32, 131.36 (q, J = 33.2 Hz), 124.39 (p, J = 3.8 Hz), 123.39 (d, J = 272.8 Hz), 71.74, 24.62. 19 F NMR (376 MHz, chloroform-d) δ -63.33. 11 B NMR (160 MHz, chloroform-d) δ 41.80.

[0075] Synthesis procedure - Preparation of catalyst Catalyst sample C1, tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct was prepared as follows.

[0076] Preparation of lithium isopropoxytri(3,5-bis(trifluoromethyl)phenyl)borate

[0077]

Chemical formula

[0078] Preparation of Tris(3,5-bis(trifluoromethyl)phenyl)borane THF Adduct

[0079]

Chem.

[0080] A portion of the solid (4.041 g) was dissolved in ether (100 mL) and THF (5 mL) was added. The volatiles were removed from the reaction mixture under reduced pressure. The residue was extracted with benzene, filtered, and the volatiles were removed from the reaction mixture under reduced pressure to give the THF-adduct product as a colorless solid, 4.10 g, 91.3%. THF Adduct: 1 H NMR (400 MHz, benzene-d6) δ 7.80 - 7.78 (m, 6H), 7.72 (dq, J = 1.8, 0.9 Hz, 3H), 2.90 - 2.83 (m, 4H), 0.57 - 0.49 (m, 4H). 13 C NMR (101 MHz, benzene-d6) δ 148.11, 133.40, 131.38 (q, J = 32.5 Hz), 124.21 (q, J = 272.8 Hz), 121.37 (p, J = 4.1 Hz), 74.14, 23.94 (d, J = 2.7 Hz). 19 F NMR (376 MHz, benzene-d6) δ -62.95. 11 B NMR (160 MHz, benzene-d6) δ 11.84.

[0081] Catalyst Sample C2, bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct was prepared as follows.

[0082] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane

[0083]

Chemical formula

[0084] The catalyst sample C3, bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct was prepared as follows.

[0085] Preparation of lithium bis(diethyl etherate)bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)-isopropoxyborate

[0086]

Chemical formula

[0087] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoroborane)

[0088]

Chemical formula

[0089] Preparation of the THF Adduct of Bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane

[0090]

Chem.

[0091] The catalyst sample C4, bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)THF adduct was prepared as follows.

[0092] Preparation of lithium bis(diethyl etherate)bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)isopropoxyborate

[0093]

Chemical formula

[0094] Preparation of THF Adduct of Bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane

[0095]

Chem.

[0096] Catalyst sample C5, bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane was prepared as follows.

[0097] Preparation of lithium isopropoxybis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0098] [Chemical formula] To a cold (-78 °C, CO2(s) bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (3.00 g, 10.24 mmol) in diethyl ether (200 mL), n-butyllithium (4.00 mL, 2.535 M in hexane, 10.14 mmol) was slowly added dropwise. The reaction mixture was stirred at -78 °C for 1 hour. Isopropoxybis(3,5-bis(trifluoromethyl)phenyl)borane (5.036 g, 10.15 mmol) in ether (18 mL) was slowly added. The reaction mixture was stirred at -78 °C for several hours. The solution was warmed to ambient temperature with stirring overnight to obtain a pale yellow transparent solution. Volatiles were removed from the reaction mixture to obtain a yellow oil. The oil was extracted with benzene. There was no insoluble matter. Volatiles were removed from the reaction mixture to obtain a yellow oil. The yield was 7.88 g, 98.3%. 1 1H NMR (400 MHz, benzene-d6) δ 8.06 (s, 1H), 8.00 (s, 4H), 7.70 (dt, J = 1.8, 0.9 Hz, 2H), 7.40 (d, J = 8.3 Hz, 1H), 7.19 (d, J = 8.4 Hz, 1H), 3.79 (hept, J = 6.1 Hz, 1H), 2.78 (q, J = 7.1 Hz, 4H), 0.73 (d, J = 6.1 Hz, 6H), 0.54 (t, J = 7.1 Hz, 6H). 1313C NMR (101 MHz, benzene-d6) δ 158.31, 153.97, 135.44 (q, J = 3.7 Hz), 135.23, 133.55 (t, J = 4.1 Hz), 133.25, 133.18, 132.37 (d, J = 97.8 Hz), 130.92 (q, J = 32.0 Hz), 127.80 (q, J = 273.9 Hz), 124.92 (q, J = 272.5 Hz), 124.66 (q, J = 272.8 Hz), 123.86 (q, J = 3.8 Hz), 119.86 (p, J = 3.9 Hz), 66.24, 66.17, 25.60, 13.94. 19 19F NMR (376 MHz, benzene-d6) δ -55.30--55.51 (m), -62.82, -63.61. 11 11B NMR (160 MHz, benzene-d6) δ 2.16.

[0099] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane

[0100]

Chemical formula

[0101] The catalyst sample C6, (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane was prepared as follows.

[0102] Preparation of lithium diisopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0103] [Chemical formula] n-Butyllithium (4.00 mL, 2.535 M in hexanes, 10.14 mmol) was added dropwise to a stirred solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (3.000 g, 10.24 mmol) in diethyl ether (150 mL) cooled to between -101 °C and -99 °C (CO2(s), then N2(l), methanol bath). The reaction mixture was stirred at approximately -100 °C for 2 h and then warmed to -78 °C. Bis(isopropoxy)(3,5-bis(trifluoromethyl)phenyl)borane (3.510 g, 10.26 mmol) in ether (10 mL) was added slowly. The reaction mixture was warmed to ambient temperature with stirring overnight. Volatiles were removed under reduced pressure from the pale yellow, almost clear solution to afford a solid that appeared crystalline. The solid was dissolved in ether (10 mL) and placed in the freezer. Nothing precipitated. The ether was evaporated and the yellow solid was dissolved in hexanes, filtered, and concentrated under a stream of nitrogen to afford a crystalline solid. The supernatant was removed and the solid was dried under reduced pressure. Yield of colorless crystals from the first harvest: 3.318 g. NMR analysis of the crystals indicated pure desired compound. The supernatant was placed in the freezer overnight. Crystalline material formed. The supernatant was removed by pipette and discarded. The crystalline residue was dried under reduced pressure: 2.017 g. Total yield: 5.335 g, 82.79%. 1 H NMR (400 MHz, benzene-d6) δ 8.39 (s, 2H), 8.26 (s, 1H), 7.90 (dq, J = 1.8, 0.9 Hz, 1H), 7.56 (d, J = 8.2 Hz, 1H), 7.27 (ddt, J = 7.9, 1.7, 0.8 Hz, 1H), 3.18 (hept, J = 6.0 Hz, 2H), 2.92 (q, J = 7.1 Hz, 4H), 0.89 (t, J = 7.1 Hz, 6H), 0.78 (d, J = 6.1 Hz, 6H), 0.68 (d, J = 6.0 Hz, 6H). 1313C NMR (101 MHz, benzene-d6) δ 153.10, 136.65 (q, J = 29.6 Hz), 134.81 (dd, J = 2.7 Hz, 1.9 Hz), 133.93 (q, J = 3.6 Hz), 131.93 (q, J = 31.6 Hz), 131.35, 129.76 (q, J = 31.9 Hz), 127.26 (q, J = 274.6 Hz), 125.17 (d, J = 272.4 Hz), 124.89 (q, J = 272.8 Hz), 123.25 (q, J = 3.9 Hz), 119.89 (p, J = 3.9 Hz), 66.42, 64.08, 25.49, 24.57, 14.36. 19 19F NMR (376 MHz, benzene-d6) δ -55.79, -62.66, -63.30. 11 11B NMR (160 MHz, benzene-d6) δ 5.32.

[0104] Preparation of Isopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane

[0105]

Chemical formula

[0106] Preparation of Lithium Isopropoxybis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borate

[0107] [Chemical formula] To a cold (-78 °C, CO2(s) bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (1.800 g, 6.14 mmol) in diethyl ether (150 mL), n-butyllithium (2.40 mL, 2.535 M in hexane, 6.08 mmol) was slowly added dropwise. The reaction mixture was stirred at -78 °C for 1 hour. Isopropoxy(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borane (3.022 g, 6.09 mmol) in ether (18 mL) was slowly added. The reaction mixture was stirred at -78 °C for several hours. The solution was warmed overnight with stirring to ambient temperature to obtain a pale yellow transparent solution. Volatiles were removed from the reaction mixture to give a yellow oil. The oil was extracted with benzene. There was no insoluble matter. Volatiles were removed from the reaction mixture to give a yellow oil. The yield was 4.21 g, 87.6%. 1 1H NMR (400 MHz, benzene-d6) δ 8.30 (s, 2H), 8.12 (s, 2H), 7.65 (dt, J = 1.7, 0.9 Hz, 1H), 7.27 (d, J = 8.2 Hz, 2H), 7.08 (d, J = 8.2 Hz, 2H), 3.87 (hept, J = 6.2 Hz, 1H), 2.91 (q, J = 7.1 Hz, 4H), 0.65 (d, J = 6.2 Hz, 6H), 0.63 (t, J = 7.1 Hz, 6H). 1313C NMR (101 MHz, benzene-d6) δ 157.17, 156.73, 134.42, 133.88 (q, J = 3.6 Hz), 133.04 (d, J = 28.4 Hz), 132.88 (q, J = 32.1 Hz), 129.95 (q, J = 31.9 Hz), 127.74 (q, J = 273.6 Hz), 127.33 (q, J = 6.9 Hz), 124.97 (q, J = 272.4 Hz), 124.50 (q, J = 273.0 Hz), 122.72 (q, J = 3.8 Hz), 118.78 (p, J = 4.1 Hz), 65.88, 65.34, 25.11, 13.91. 19 19F NMR (376 MHz, benzene-d6) δ -56.31, -62.89, -63.76. 11 11B NMR (160 MHz, benzene-d6) δ 2.98.

[0108] Preparation of bis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borane

[0109]

Chemical formula

[0110] Catalyst sample C7 was prepared as follows.

[0111] Preparation of tris(2,5-bis(trifluoromethyl)phenyl)borane

[0112]

Chemical formula

[0113] Catalyst sample C8, bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct was prepared as follows.

[0114] Preparation of Lithium(Tetrahydrofranate)Bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)Isopropoxyborate __________________ 2 Herrington,T.J.;Thom,A.J.W.;White,A.J.P.;Ashley,A.E.Dalton Trans.2012,41,9019.

[0115] [Chemical formula] n-Butyllithium (3.00 mL, 2.54 M in hexane, 7.61 mmol) was added dropwise with stirring to a solution of 1-bromo-2,3,5,6-tetrafluoro-4-trifluoromethylbenzene (2.26 g, 7.61 mmol) in diethyl ether (100 mL) cooled to -101 °C to -99 °C (CO2(s), then N2(l), methanol bath). The reaction mixture was stirred at -100 °C for 2 hours and then warmed to -76 °C. Bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane (3.78 g, 7.61 mmol) in ether (10 mL) was added slowly to the reaction mixture. The reaction mixture was warmed slowly overnight with stirring to ambient temperature. The next day, the pale yellow almost clear solution was filtered and the volatiles were removed under reduced pressure to give a solid that appeared crystalline. The solid was washed with hexane, filtered, and dried under reduced pressure. An aliquot of the solid was removed for NMR analysis. The solubility of the solid aliquot in benzene was limited. The aliquot was dissolved in THF, the volatiles were removed under reduced pressure, and then it was analyzed again by NMR in benzene. Yield: 6.16 g, 93.2%. 1 1H NMR (500 MHz, benzene-d6) δ 8.32 (s, 4H), 7.85 (s, 2H), 3.47 (h, J = 6.2 Hz, 1H), 3.26 - 3.17 (m, 4H), 1.24 - 1.16 (m, 4H), 0.55 (d, J = 6.2 Hz, 6H). 1313C NMR (126 MHz, benzene-d6) δ 144.07 (d, J = 259.4 Hz), 134.41, 133.82, 133.48 (d, J = 187.5 Hz), 130.59 (q, J = 32.2 Hz), 130.45 (q, J = 31.8 Hz), 126.40 - 123.43 (m), 125.84, 124.97 (q, J = 272.4 Hz), 119.94 (p, J = 4.0 Hz), 118.92 (d, J = 190.9 Hz), 109.57 (d, J = 22.7 Hz), 68.38, 65.30, 25.64, 25.13. 19 19F NMR (470 MHz, benzene-d6) δ -56.26 (t, J = 20.7 Hz), -62.59, -137.04, -141.73. 11 11B NMR (160 MHz, benzene-d6) δ 1.20.

[0116] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane tetrahydrofuranate, THF adduct

[0117] [Chemical formula] To a solution of lithium(tetrahydrofuranate)bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)isopropoxyborate (6.16 g, 7.10 mmol) in diethyl ether (100 mL) was added chlorotrimethylsilane (2.00 mL, 18.4 mmol) with stirring. The reaction mixture was stirred overnight. The next day, 19 Analysis of an aliquot of the reaction mixture by 19F NMR spectroscopy revealed that no reaction had occurred. A solution of hydrogen chloride in ether (7.00 mL, 2.0 M, 14.0 mmol) was added, and the reaction mixture was stirred overnight. The next day, 19Analysis of an aliquot of the reaction mixture by 19F NMR spectroscopy revealed that the reaction was complete. The mixture was filtered and volatiles were removed from the filtrate under reduced pressure. The resulting residue was dissolved in toluene, filtered, and volatiles were removed from the filtrate under reduced pressure to give 4.50 g of a crude product. The colorless paste-like solid was washed with hexane, filtered to give a colorless powder, which was dried under reduced pressure. NMR analysis of the powder revealed that one molecule of isopropanol remained in the coordination sphere of borane. Yield as the isopropanol adduct of borane: 2.45 g, 52.8%.

[0118] A portion (1.811 g) of the borane isopropanol adduct was dissolved in ether (40 mL) and THF (10 mL) was added to the solution. The solution was slowly evaporated to give large crystals. The supernatant was removed and the very pale yellow crystals were washed with hexane. The crystals were dried under reduced pressure (1.08 g). The crystals were analyzed by X-ray crystallography and found to be the borane isopropanol adduct. THF did not displace the coordinated alcohol. The supernatant solution from the crystals and the hexane washings were combined and concentrated under vacuum to give a second harvest of crystals (0.422 g). The second harvest of crystals was washed and dried in the same manner as the first harvest. NMR analysis indicated the presence of coordinated isopropanol but little or no presence of THF. THF was added and then volatiles were removed under reduced pressure. NMR analysis indicated the presence of THF but still some presence of isopropanol was indicated. The solid was dissolved in THF and then pumped off. This was repeated 5 more times to give the THF adduct of the product as a white powder. Yield: 0.413 g, 22.4%.

[0119] THF adduct: 1 1H NMR (400 MHz, benzene-d6) δ 7.87 (s, 4H), 7.80 (s, 4H), 3.02 - 2.93 (m, 4H), 0.78 - 0.72 (m, 4H). 1313C NMR (126 MHz, benzene-d6) δ 147.98 (td, J = 16.5, 3.6 Hz), 146.05 (tt, J = 11.8, 4.1 Hz), 145.58 (d, J = 20.9 Hz), 143.50 (d, J = 20.1 Hz), 133.44, 131.39 (q, J = 32.6 Hz), 124.24 (q, J = 272.7 Hz), 121.78 (t, J = 4.0 Hz), 121.45 (q, J = 274.4 Hz), 109.38 - 108.10 (m), 73.75, 23.90. 19 19F NMR (376 MHz, benzene-d6) δ -56.57 (t, J = 21.0 Hz), -62.95, -130.60 (dd, J = 22.5, 13.2 Hz), -140.71 (qt, J = 19.7, 8.6 Hz). 11 11B NMR (160 MHz, benzene-d6) δ 7.22.

[0120] The catalyst sample prepared as described above in Reference Example 2 is shown below.

[0121]

Chemical formula

[0122] Structures of fluorinated arylborane Lewis acid catalyst samples C1 - C8 and commercially available FAB are shown above. Structure C1 corresponds to tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct (starting material A1 of the claim). Structure C2 corresponds to bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct (starting material A2 of the claim). Structure C3 corresponds to bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct (starting material A3 of the claim). Structure C4 corresponds to bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct (starting material A4 of the claim). Structure C5 corresponds to bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane (starting material A5 of the claim). Structure C6 corresponds to (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane (corresponding to starting material A6 of the claim). Structure C7 for comparison is tris(2,5-bis(trifluoromethyl)phenyl)borane. Structure C8 corresponds to bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct (starting material A7 of the claim).

[0123] Reference Example 3 - Screening Study The fluorinated triarylborane Lewis acid prepared as described above was evaluated for SiH coupling in the presence of water as follows. In a nitrogen-purged glove box, a solution of the fluorinated triarylborane Lewis acid sample shown above was prepared in a 10 mL glass vial (e.g., 30.7 mg of FAB was dissolved in 5 mL of toluene). Silane (e.g., TES, 38.4 μL, 2 equivalents), internal standard (IS, mesitylene, 16.8 μL, 1 equivalent) were placed in an NMR tube. The catalyst (0.5 mL, 5 mol%) was delivered as a toluene stock solution via a pipette. The tube was capped, 11H NMR spectra were measured at regular time intervals. The conversion was established at 2 and 24 h by comparison to an internal standard (Si-H bond vs. IS, or product vs. IS if possible).

[0124] [Chemical formula]

[0125] [Table 2]

[0126] While not wishing to be bound by theory, C7 is thought to be too sterically bulky to catalyze the SiH coupling reaction under the conditions tested, demonstrating that not all fluorinated aryl boranes catalyze this reaction.

[0127] General procedure for the preparation of reference example 4 - SiH-containing polyolefin copolymers (copolymers of ethylene, octene, and 5-hexenyldimethylsilane (HDMS) or 7-octenyldimethylsilane (ODMS)) Batch reactor polymerizations were conducted in a 2 L Parr batch reactor. The reactor was heated by an electric heating mantle and cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating / cooling system were controlled and monitored by a CAMILE TG process computer. A dump valve was attached to the bottom of the reactor to transfer the reactor contents to a stainless-steel dump pot. The dump pot was vented to a 30 gallon blowdown tank, and both the pot and the tank were purged with nitrogen. Prior to use, all solvents to be used for polymerization or catalyst replenishment were passed through a solvent purification column to remove any impurities that could affect the polymerization. 1-Octene and ISOPAR-E were passed through two columns, a first column containing A2 alumina and a second column containing Q5 reactant. (ISOPAR-E is an isoparaffin fluid commercially available from ExxonMobil Chemical Company that typically contains less than 1 ppm benzene and less than 1 ppm sulfur.) Ethylene was passed through two columns, a first column containing A204 alumina and a 4 Å molecular sieve and a second column containing Q5 reactant. The N2 used for transfer was passed through a single column containing A204 alumina, a 4 Å molecular sieve, and Q5 reactant.

[0128] The desired amount of 5-hexenyldimethylsilane monomer or 7-octenyldimethylsilane monomer was added to the filling column via a shot tank, followed by the addition of ISOPAR-E solvent and / or 1-octene depending on the desired reactor fill level. A laboratory scale with the filling column attached was used to fill the filling column to the fill level set point. After the liquid feed addition, the reactor was heated to the polymerization temperature set point. When ethylene was used, ethylene was added to the reactor while the reactor was at the reaction temperature to maintain the reaction pressure set point. The ethylene addition rate was monitored with a Micromotion flow meter.

[0129] The scavenger MMAO-3A was treated inside an inert atmosphere glove box, drawn into a syringe, and transferred under pressure to the catalyst shot tank. Subsequently, after rinsing three times with 5 mL of toluene each time, it was injected into the reactor. The precatalyst and activator were mixed with an appropriate amount of purified toluene to obtain a solution with the desired molar concentration. The catalyst and activator were treated inside an inert atmosphere glove box, drawn into a syringe, and transferred under pressure to the catalyst shot tank. Subsequently, it was rinsed three times with 5 mL of toluene each time. The experimental timer was started immediately after the catalyst addition. When ethylene was used, ethylene was added by CAMILE to maintain the reaction pressure set point inside the reactor. These polymerizations were carried out for 10 minutes, then the stirrer was stopped and the bottom dump valve was opened to transfer the reactor contents to the dump pot. The dump pot contents were poured into a tray placed in the laboratory hood, where the solvent was allowed to evaporate overnight. Then, the tray containing the remaining polymer was transferred to a vacuum oven, where they were heated to 140 °C under vacuum to remove any remaining solvent. After cooling the tray to ambient temperature, the polymer was weighed for yield / efficiency and subjected to polymer tests.

[0130] The copolymer samples were prepared according to the batch reactor process using the following conditions: For the first copolymer in Table 3, 120 °C, 12 g ethylene charge, 3.5 mL 5-hexenyl dimethylsilane, 52 g 1-octene, 588 g ISOPAR E, 20 μmol MMAO-3A, 1.2 equivalents of bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate per 1.0 equivalent of procatalyst; for the second copolymer in Table 3, 120 °C, 12 g ethylene charge, 4 mL 7-octenyl dimethylsilane, 58 g 1-octene, 596 g ISOPAR-E, 20 μmol MMAO-3A, 1.2 equivalents of bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate per 1.0 equivalent of procatalyst; and for the third copolymer in Table 3, 120 °C, 12 g ethylene charge, 4 mL 7-octenyl dimethylsilane, 58 g 1-octene, 592 g ISOPAR-E, 20 μmol MMAO-3A, 1.2 equivalents of bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate per 1.0 equivalent of procatalyst. The amount of procatalyst used was adjusted to achieve the desired efficiency. Ethylene was fed during the polymerization and the reactor was cooled as necessary to maintain the reactor pressure and temperature constant. The polymerization was carried out until 23 g of ethylene was incorporated. All polymerizations were carried out using bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate as the activator and MMAO as the scavenger. The properties of the silicone-polyolefin copolymer (elastomer) are shown in Table 3.

[0131]

Table 3

[0132] Crosslinking Study Using a SiH-Functional Polyolefin Copolymer in Reference Example 5 Samples of fluorinated triarylborane Lewis acids C4, C5, C6, and C7 prepared as described above were selected to determine their feasibility to catalyze the reaction of silicon-bonded hydrogen atoms in copolymers of ethylene, 1-octene, and either HDMS or ODMS prepared as described in Reference Example 4. Commercially available tris(pentafluorophenyl)borane (FAB) was used as a control.

[0133] Solutions of these fluorinated triarylborane Lewis acids (boranes) were first prepared by weighing the solid borane in a glove box under a nitrogen atmosphere. The borane was then removed from the glove box and mixed with a known mass of toluene to produce a solution that could be blended into the molten copolymer. Care was taken to limit the exposure time to air before solution preparation, and dried toluene passed through a molecular sieve was used as the solvent. All tests of the catalyst-containing elastomer samples were initiated within 48 hours after removing the catalyst samples from the nitrogen atmosphere to limit air or moisture contamination. Solutions of C4, C5, C6, and C7 were added to the melt blending process such that the loading of each borane was 100 ppm. Melt blending was carried out using a Haake blender with a 20 g bowl, setting the temperature to 80 °C, and using a blend speed of 60 rpm. 10 g of the elastomer described in Table 3 was blended for 3 minutes until fully melted, and then 100 μL of the borane solution was added. The system was blended for an additional 3 minutes until thoroughly homogenized, and then the resulting catalyst-containing elastomer was removed and cooled. There was no visual evidence of premature crosslinking of the elastomer during melt blending with the C4, C5, C6, and C7 solutions. When the FAB solution was used in the same process, premature crosslinking was visually observed.

[0134] Next, the obtained catalyst-containing elastomer was compression-molded into torsion bars (thickness 2 mm) by compression-molding at 90 °C for 4 minutes with a force of 20,000 lbs. Subsequently, these torsion bars were moisture-cured by exposing them to a humid environment controlled at 85 °C, 85% relative humidity, or 25 °C, 85% relative humidity. After 1 day or 5 days, the bars were removed from the humid environment, giving some idea about the kinetics of the moisture-curing reaction. After removing the bars from the humid environment and testing them, they were discarded and not used for further testing.

[0135] Reference Example 6 - Analysis of Samples The torsion bars were tested via dynamic mechanical analysis (DMA) using an ARES rheometer. The samples were fixed to the instrument and exposed to a temperature sweep from 25 °C to 250 °C, a temperature gradient of 2 °C / min, and a strain of 1%. Moisture-curing crosslinking was monitored by evidence of a temperature-insensitive storage modulus plateau.

[0136] The DMA shear storage modulus of the sample containing C4 borane with 1-day moisture exposure at 85 °C decreased monotonically with temperature and decreased to approximately 10 2 Pa at 250 °C, indicating that minimal crosslinking occurred during the exposure. The DMA shear storage modulus of the sample after 5 days of moisture exposure decreased with temperature until the sample reached approximately 160 °C. Then, the sample showed a shear storage modulus plateau of approximately 10 4 Pa, indicating that a crosslinked network was formed, preventing further melting of the sample with increasing temperature. This test demonstrated the effectiveness of C4 borane for use as a latent condensation catalyst in polymer systems.

[0137] The DMA shear storage modulus of the sample containing C5 borane with 1-day moisture exposure at 85 °C decreased monotonically with temperature and decreased to approximately 10 4 Pa at 250 °C, indicating that minimal crosslinking occurred during the exposure. The DMA shear storage modulus of the sample after 5 days of moisture exposure decreased with temperature until the sample reached 170 °C.

[0138] Next, the sample exhibited a shear storage modulus plateau of approximately 10 4 Pa, indicating that some crosslinking had occurred and preventing further melting of the sample with increasing temperature. This test demonstrated the effectiveness of C5 borane for use as a latent condensation catalyst in polymer systems.

[0139] The DMA shear storage modulus of the sample containing C6 borane with 1-day moisture exposure at 85 °C decreased monotonically with temperature and decreased to approximately 10 3 Pa at 250 °C, indicating that minimal crosslinking occurred during the exposure. The DMA shear storage modulus of the sample after 5-day moisture exposure decreased with temperature until the sample reached approximately 160 °C. Next, the sample exhibited a shear storage modulus plateau of approximately 10 4 Pa, indicating that a crosslinked network was formed and preventing further melting of the sample with increasing temperature. This test demonstrated the effectiveness of C6 borane for use as a latent condensation catalyst in polymer systems.

[0140] The DMA shear storage modulus of the sample containing C5 borane with 1-day and 5-day moisture exposure at 25 °C decreased monotonically with temperature, and the degree of decrease was the same as that of the sample without moisture treatment, indicating that minimal crosslinking occurred during moisture exposure at 25 °C. By comparing with the test of the C5-containing sample by moisture exposure at 85 °C, this test demonstrated that heating is required for C5 as a latent condensation catalyst to effectively cure polymer systems.

[0141] The DMA shear storage modulus of the sample containing C7 with 1-day and 5-day moisture exposure at both 25 °C and 85 °C decreased monotonically with temperature, and the degree of decrease was the same as that of the sample without moisture treatment, indicating that minimal crosslinking occurred during moisture exposure at 25 °C and 85 °C. These two tests demonstrated that C7 does not act sufficiently as a catalyst both below and above the melting point of the polymer system under the tested conditions.

[0142] The torsion bar was analyzed using ATR FT-IR spectroscopy at the time of interest to monitor the formation of Si-0-Si bonds and the loss of Si-H bonds. The characteristic vibration frequencies monitored for this study are summarized in Table 4.

[0143]

Table 4

[0144] The spectra of the boranes (C4 and C5) analyzed showed an increasing trend in the siloxane peak region (1000 - 1130 cm -1 ) as a function of time. Two peaks (890 cm -1 and 2080 - 2280 cm -1 ) associated with Si-H vibrations also decreased over longer times, indicating the loss of Si-H bonds. The combination of these observations led to the conclusion that at least some of the Si-H groups reacted to give siloxane bonds (Si-0-Si bonds). The appearance of unexpected peaks in both cases at about 1710 cm -1 suggests that further side reactions may have occurred. Also, a significant amount of unreacted Si-H content still remained in this system, which was observed to be either able to continue reacting over a longer period or too immobile in the partially cross-linked matrix to have the mobility to complete cross-linking reactions with other unreacted Si-H groups. Further fillings of these boranes were not tested, but higher fillings are hypothesized to result in more complete utilization of the Si-H content of the copolymer and a greater corresponding cross-link density.

[0145] These boranes present a practical controllable pathway to enable the moisture curing of Si-H containing copolymers. The FTIR spectra revealed little change in the SiH peaks in the C7 sample over time, which was consistent with model system studies where C7 did not catalyze any conversion of SiH under the tested conditions.

[0146] Industrial Applicability As demonstrated in the examples shown above, when starting material B) comprises a silyl hydride functional polyolefin, starting materials A) and B) can be combined, for example, mixed, and will not cure until they are exposed to water. The ability to combine and store the silyl hydride (SiH functional material) and the catalyst prior to use / cure is an unexpected advantage of the compositions and methods described herein.

[0147] Problems to be Solved by the Invention The catalysts mainly used in the preparation of both siloxane intermediates and siloxane cured networks from Si-H functional silanes and siloxanes are platinum-based catalysts, which have the specific drawbacks described above. A new alternative to Pt-based catalysts is the use of tris(pentafluorophenyl)borane (B(C6F5)3), which is referred to herein as FAB. FAB is relatively low-cost, does not contain heavy metals, and has a low level required for catalysis. The use of FAB as a catalyst has been reported in the reaction between a Si-H functional group and another functional group useful in curable siloxane compositions or as an intermediate. These functional groups include alkoxysilyl functional groups (≡Si-OR) and silanols (≡Si-OH).

[0148] In the case of the FAB-catalyzed coupling reaction between ≡Si-H and ≡Si-OR or between ≡Si-H and ≡Si-OH, one major limitation for commercial use is that the reaction is highly exothermic and occurs very rapidly at room temperature. From the perspective of large-scale production of siloxanes, this is a problem due to 1) the rapid generation of flammable gas and 2) the rapid heating of the reaction mixture. The combination of these factors makes it difficult to control the implementation on a commercial scale, difficult to achieve proper reaction feed / mixing and monitoring, and may result in poor reproducibility.

[0149] An alternative catalyst that can promote the reaction between two Si-H moieties in the presence of water in a more controlled manner than FAB is needed in the industry. It is particularly desirable to have the ability to control its rate based on the choice of catalyst.

[0150] Solution The compositions and methods described herein use fluorinated triarylborane Lewis acids as catalysts. These fluorinated triarylborane Lewis acids provide better reaction rate control than FAB.

[0151] Definition and Use of Terms The abbreviations used herein have the definitions in Table 5 below.

[0152] [Table 5]

[0153] All amounts, ratios, and percentages are by weight unless otherwise indicated. The amounts of all starting materials in the composition total 100% by 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. The disclosure of a range includes the range itself, anything included within the range, and the endpoints. For example, the disclosure of the range 2.0 - 4.0 includes not only the range 2.0 - 4.0, but also 2.1, 2.3, 3.4, 3.5, and 4.0 individually, and any other numbers included within the range. Further, for example, the disclosure of the range 2.0 - 4.0 includes subsets such as 2.1 - 3.5, 2.3 - 3.4, 2.6 - 3.7, and 3.8 - 4.0, and any other subsets included within the range. Similarly, the disclosure of a Markush group includes the entire group and any individual elements and subgroups included therein. For example, the disclosure of the Markush group "hydrogen atom, alkyl group, alkenyl group or aryl group" includes the individual alkyls that are its elements, the alkyl and aryl that are subgroups, and any other individual elements and subgroups included within the Markush group.

[0154] The terms "comprising" and its derivatives, such as "comprise" and "comprises", are used herein in their broadest sense to mean "including", "include", "consist(ing) essentially of", and "consist(ing) of", and are used inclusively. The use of "for example", "e.g.", "such as", and "including" to list 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.

[0155] Generally, as used herein, the hyphen "-" or 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". Each of the foregoing patent applications, patents, and / or patent publications is hereby expressly incorporated by reference in its entirety into this specification on an individual basis for one or more non-limiting embodiments.

[0156] It is to be understood that the appended claims are not limited to the specific compounds, compositions, or methods described in the "Detailed Description of the Invention" and may vary between specific embodiments within the scope of the appended claims.

Claims

1. A composition comprising: A) a fluorinated triarylborane Lewis acid selected from the group consisting of: A1) tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct; A2) bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct; A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct; A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane; A6) (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane; and A8) a fluorinated triarylborane Lewis acid selected from the group consisting of two or more combinations of A1), A2), and A4)-A6); and B) a silyl hydride having at least one silicon-bonded hydrogen atom per molecule.

2. A) is A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct; A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane; and A6) (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane, the composition according to claim 1.

3. B) the silyl hydride is B1) Formula H ｋ SiR ５ （４－ｋ） [In the formula, each R ５ is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, and the subscript k is 1 to 3] silane, B2) 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 [wherein each R ４ is an independently selected monovalent hydrocarbon group that does not contain aliphatic unsaturation], a polyorganohydrogensiloxane containing two or more siloxane units selected from the group consisting of, and B3) of formula (B3-1): 【Chemical 1】 [Wherein each R １ is a monovalent hydrocarbon group independently selected, and each subscript a is independently 1 or 2], a polyolefin having a silicon-bonded hydrogen functional group, the composition according to claim 1 or 2, selected from the group consisting of.

4. B1) is a silane of the formula HSiR ５ ３ [wherein each R ５ is an alkyl group having 1 to 6 carbon atoms], and B2) is a 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 [wherein, R ４ is as described above, and the subscripts g, h, i, and j have values such that g≥0, h≥0, the quantity (g + h) has an average value of 2, i≥0, j≥0, and the quantity (g + j)≥1, and the quantity (i + j) is in the range of 0 to 1000] is a polydiorganohydrogensiloxane, B3) is the unit formula (B3-2): [Chemical Formula 2] [wherein, R １ and the subscript a are as described above, and each D １ is independently a divalent hydrocarbon group having 2 to 50 carbon atoms, and each R ２５ is independently H, a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 18 carbon atoms, and the subscripts M and N have values such that 1 ≦ M ≦ 10 and 10 ≦ N ≦ 20,000], Unit formula (B3-3): 【Chemical Formula 3】 [wherein, subscripted letters a and R １ are as described above, subscripted letter f is 0 or 1, subscripted letters t and u are ratios having relative values such that 0 < t ≦ 1 and 0 ≦ u ≦ 1, subscripted letter g is 1 or more, and each R ｅｔ represents an ethylene unit, and each R Ｏ represents an olefin unit other than ethylene], and Unit formula (B3-4): 【Chemical Formula 4】 [wherein the subscripted letters a, f, g, t, and u, and R １ are as described above, and each R ７ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms], the composition according to claim 3, which is a SiH-functional polyolefin selected from the group consisting of

5. A method for forming a product having a siloxane bond, the method comprising: １） A) a fluorinated triarylborane Lewis acid selected from the group consisting of: A1) tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct; A2) bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct; A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct; A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane; A6) (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane; and A fluorinated triarylborane Lewis acid selected from the group consisting of two or more combinations of A8), A1), A2), and A4)-A6), and B) a silyl hydride having at least one silicon-bonded hydrogen atom per molecule, C) water, are combined, reacting the silicon-bonded hydrogen atom to form a by-product containing the siloxane bond and hydrogen. A method comprising the steps of

6. The starting material A) is A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct, A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane, and The method according to claim 5, selected from the group consisting of A6) (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane.

7. B) The silyl hydride is B1) Formula H ｋ SiR ５ （４－ｋ） [wherein each R ５ is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, and the subscript k is 1 to 3] silane, B2) 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 [wherein each R ４ is an independently selected monovalent hydrocarbon group that does not contain aliphatic unsaturation] A polyorganohydrogensiloxane containing two or more siloxane units selected from the group consisting of, and B3) Formula (B3-1): [Chemical Formula 5] [wherein each R １ is an independently selected monovalent hydrocarbon group, and each subscript a is independently 1 or 2], the method according to claim 5 or 6, which is selected from the group consisting of polyolefins having a silicon-bonded hydrogen functional group.

8. The starting material B1) is a silane of the formula HSiR ５ ３ [wherein each R ５ is an alkyl group having 1 to 6 carbon atoms], and The starting material B2) has the 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 [wherein, R ４ is as described above, and the subscripts g, h, i, and j have values such that g ≧ 0, h ≧ 0, the quantity (g + h) has an average value of 2, i ≧ 0, j ≧ 0, and the quantity (g + j) ≧ 1, and the quantity (i + j) is in the range of 0 to 1000] is a polydiorganohydrogensiloxane, The starting material B3) is Unit formula (B3-2): 【Chemical Formula 6】 [In the formula, each D1 is independently a divalent hydrocarbon group having 2 to 50 carbon atoms, and R １ and the subscript a are as described above, and each R ２５ is independently H, a monovalent hydrocarbon group having 1 to 18 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 18 carbon atoms, 1 ≦ M ≦ 10, 10 ≦ N ≦ 20,000]. Unit formula (B3-3): 【Chemical Formula 7】 [wherein, subscripted letters a and R １ are as described above, subscripted letter f is from 0 to 1, subscripted letters t and u have relative values such that 0 < t ≤ 1 and 0 ≤ u ≤ 1, subscripted letter g is 1 or more, and each R ｅｔ represents an ethylene unit, and each R Ｏ represents an olefin unit other than ethylene], and Unit formula (B3-4): [Chemical 8] [wherein the subscripted letters a, f, g, t, and u, and R １ are as described above, and each R ７ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms], the method according to claim 7, which is a SiH-functional polyolefin copolymer selected from the group consisting of

9. The combination in step 1) includes the steps of mixing and heating the starting materials A), B), and C) in any order. The method according to any one of claims 5 to 8.

10. The starting material A) is dissolved in a solvent before step 1). The method according to any one of claims 5 to 9.

11. The starting materials A) and B) are combined before step 1). The method according to any one of claims 5 to 10.

12. The method according to any one of claims 5 to 11, further comprising the step of neutralizing the residual fluorinated triarylborane Lewis acid in the product.

13. After step 1) and / or after step 1), further comprising a step of removing the by-product containing H ２ The method according to any one of claims 5 to 12, further comprising a step of removing the by-product containing

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