Compositions and methods for silyl hydride reactions catalyzed by fluorinated arylborane Lewis acids

Abstract

The present invention discloses a composition comprising 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 silicon-bonded hydrogen atoms from the silyl hydride with water, thereby forming siloxane bonds in the resulting product. The composition and method can be used to form siloxane intermediates and cured networks.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit under 35 USC §119(e) of U.S. Provisional Patent Application Serial No. 63 / 043,149, filed on June 24, 2020. U.S. Provisional Patent Application Serial No. 63 / 043,149 is hereby incorporated by reference. Technical Field

[0003] A composition comprises 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 silicon-bonded hydrogen atoms from the silyl hydride with water, thereby forming siloxane bonds in the resulting product. The composition and method can be used to form siloxane intermediates and cured networks. Background Art

[0004] The catalysts predominantly employed in the preparation of siloxane intermediates and siloxane cured networks from Si-H functional silanes and siloxanes are platinum based catalysts. Due to the increasing cost of platinum (Pt) and other disadvantages such as yellowing of the cured siloxane composition or formation of a black precipitate over time, there is a need in the industry for alternatives to Pt based catalysts. Furthermore, while Pt based catalysts are effective, they may also suffer from the disadvantage of requiring high temperatures (80°C to 110°C) to achieve sufficient reactivity to catalyze the formation of siloxane bonds. Summary of the invention

[0005] A composition comprises: A) a fluorinated triarylborane Lewis acid and B) a silyl hydride. The composition can be used in a method comprising: combining A) the fluorinated triarylborane Lewis acid, B) the silyl hydride, and C) water; thereby forming a product. The product has siloxane bonds formed by the reaction of SiH moieties from the silyl hydride and the water. DETAILED DESCRIPTION

[0006] The composition comprises: A) a fluorinated triarylborane Lewis acid and B) a silyl hydride. The composition may be free of 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 under conditions (e.g., anhydrous conditions) that prevent the silicon-bonded hydrogen atoms from the silyl hydride from reacting before use.

[0007] The methods described herein include 1) combining starting materials comprising (alternatively, consisting essentially of; alternatively, consisting of): A) and B) described above and C) water under conditions that will react silicon-bonded hydrogen atoms of the starting material B) to form siloxane bonds and byproducts comprising hydrogen gas.

[0008] These conditions may include, for example, mixing in any convenient manner. Mixing may be performed using conventional mixing equipment, such as batch stirred tanks. Mixing may be performed at any convenient temperature (e.g., RT). Alternatively, when the silyl hydride selected for starting material B) is viscous, mixing under shear may be performed, for example, with an extruder. The composition may be formed, for example, by mixing starting material A) and starting material B) described above. During mixing, starting material A) and starting material B) may be heated at a temperature of 50°C to 150°C, alternatively 100°C to 125°C. Optionally, starting material D) solvent may be used to promote the combination of starting material A) and starting material B). For example, starting material A) may be dissolved in the solvent before mixing with starting material D). Without being bound by theory, it is believed that using the fluorinated triarylborane Lewis acids described herein instead of other catalysts (such as Pt-based catalysts or FAB) can provide composition stability benefits when starting material A) and starting material B) are present together prior to step 1) of the methods described herein, or even when starting material A) and starting material B) are combined with heating.

[0009] Exposing the composition comprising starting material A) and starting material B) to C) water in step 1) of the method will begin to react silicon-bonded hydrogen atoms with water to form siloxane bonds. Water can be mixed with starting material A) and starting material B) in a manner as described above, and starting material A), starting material B) and starting material C) can be combined simultaneously in step 1). Alternatively, a composition comprising starting material A) and starting material B) can be prepared before step 1), and then in step 1), the composition can be exposed to water, for example by exposure to humid air. Exposure to water can be performed at a temperature of 5°C to 150°C, alternatively RT to 150°C, alternatively 5°C to 125°C, and alternatively RT to 125°C. Without being bound by theory, it is believed that the temperature of exposure to water will depend on the selected silyl hydride. For example, when starting material B) comprises, for example, a silyl-functional polyolefin, a higher temperature (e.g., 50°C to 150°C) can be used. When the starting material B) is, for example, a silane, then lower temperatures may be sufficient. For example, the temperature may alternatively be RT to 70°C, 5°C to 70°C, alternatively 5°C to 65°C, alternatively 10°C to 60°C, alternatively 15°C to 50°C, alternatively 20°C to 35°C, alternatively 5°C to 30°C, and alternatively 30°C.

[0010] The method may also optionally include one or more additional steps. The method may also include: step 2) during and / or after step 1), removing H2 generated during the formation of the product and / or step 3) removing and / or neutralizing the residual fluorinated triarylborane Lewis acid in the product. The byproduct H2 can be removed by any convenient means such as stripping and / or combustion. Removal and / or neutralization can be performed by adding E) a neutralizing agent to the product, or alternatively adding E) a neutralizing agent to the product and optionally filtering the product subsequently. Steps 2) and 3) can be performed in any order. If there are particulate byproducts, for example due to neutralization, the method may also include step 4) after neutralization, removing particles such as aluminum oxide by any convenient means such as filtering.

[0011] Starting materials A) Catalyst

[0012] 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:

[0013] Each R o is an ortho substituent, each R m is a meta-substituent, and each R p is a para-substituent, R 2 is optional and includes a functional group or a functional polymer group; and the subscript x is 0 or 1. In the above formula, Ro1-6 Each of R m1-6 Each of the R p1-3 Each of R is independently selected from H, F or CF3; provided that: not all R o1-6 , R m1-6 and R p1-3 can all be F at the same time; not all R o1 -6 , R m1-6 and R p1-3 can be H at the same time; and when R o1-4 When two or more of them are CF3, then R o5 and R o6 are each independently selected from H or F. 2 is optional, that is, when the subscript x=1, R 2 exists, and when the subscript x=0, R 2 Does not exist. 2 It may be a Lewis base that forms a complex with a fluorinated triarylborane Lewis acid and / or a molecule or moiety that contains at least one electron pair that can be used to form a coordinate bond with a Lewis acid, and may be as described in paragraphs

[0024] to

[0025] of WO2019 / 055740 for R 4 R 2 Examples of include cyclic ethers such as tetrahydrofuran or tetrahydropyran. 2 It may be tetrahydrofuran (THF).

[0014] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 and R o6 Each of may be H. Alternatively, R o1 , R o2 , R o3 and R o4 Each of may be H. Alternatively, R o5 and R o6 Each of can be F.

[0015] Alternatively, R m1 , R m2 , R m3 , R m4 , R m5 and R m6 Each of may be CF3. Alternatively, R m1 , R m2 , R m3 and R m4 Each of may be CF3. Alternatively, R m5 and Rm6 Each of may be F. Alternatively, R m5 and R m6 Each of can be H.

[0016] Alternatively, R p1 , R p2 and R p3 Each of may be H. Alternatively, R p1 and R p2 It can be H. Alternatively, R p3 It can be F. Alternatively, R p3 It can be CF3.

[0017] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R o6 , R p1 , R p2 and R p3 Each of may be H; and R m1 , R m2 , R m3 , R m4 , R m5 and R m6 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material A) may comprise tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct.

[0018] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R o6 , R m5 , R m6 , R p1 and R p2 Each of may be H; and R m1 , R m2 , R m3 , R m4 and R p3 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct.

[0019] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , Rp1 and R p2 Each of can be H; R o5 , R o6 and R p3 Each of may be F; and R m1 , R m2 , R m3 , R m4 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct.

[0020] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 , R p2 and R p3 Each of can be H; R o5 and R o6 can be F; and R m1 , R m2 , R m3 and R m4 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct.

[0021] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R m6 , R p1 , R p2 and R p3 Each of may be H; and R m1 , R m2 , R m3 , R m4 , R m5 and R o6 Each of may be CF3. The subscript x may be 0. Alternatively, the starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane.

[0022] Alternatively, R m1 , R p1 , R o2 , R o3 , R o4 , R p2 , Rp3 , R o5 and R m6 Each of may be H; and R o1 , R m2 , R m3 , R m4 , R o6 and R m5 Each of may be CF3. The subscript x may be 0. Alternatively, the starting material A) may comprise (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane.

[0023] Alternatively, R o1 , R o2 , R o3 , R o4 , R p1 and R p2 Each of can be H; R o5 , R o6 , R m5 and R m6 Each of may be F; and R m1 , R m2 , R m3 , R m4 and R p3 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct.

[0024] 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 A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane THF adduct; A6) bis(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 A8) a combination of two or more of A1) to A7). Alternatively, the fluorinated triaryl borane Lewis acid may be selected from the group consisting of: A2), A3), A4), A5), A6), A7) and a combination of two or more of A2) to A7). Alternatively, the fluorinated triaryl borane Lewis acid may be selected from the group consisting of: A4), A5), A6) and a combination 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).

[0025] Fluorinated triarylborane Lewis acids are known in the art and can be prepared by known methods, such as those disclosed in WO2019 / 055740, in particular paragraphs

[0052] to

[0096] , by modifying appropriate starting materials.

[0026] The amount of starting material A) will depend on the type and amount of other starting materials used, however, based on the combined weight of starting material A) and starting material B) in the composition, starting material A) may be present in an amount of 0.5 ppm to 5 mol%, alternatively 5 ppm to 6000 ppm. Alternatively, based on the same basis, the amount may be 5 ppm to 600 ppm, alternatively 5 ppm to 500 ppm, and alternatively 5 ppm to 100 ppm.

[0027] B) Silyl hydride

[0028] The 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 more than one SiH per molecule. The silyl hydride used herein is capable of forming a siloxane bond in the presence of A) a fluorinated triaryl borane Lewis acid and C) water. The silyl hydride containing multiple Si-H bonds may be capable of self-crosslinking in the presence of A) a fluorinated triaryl borane Lewis acid and C) water. The starting material B) may be selected from the group consisting of: B1) silane, B2) polyorganohydrogensiloxane, B3) silyl functional polyolefin and B4) a combination of two or more of B1), B2) and B3).

[0029] The silyl hydride may be B1) a silane (e.g., having one silicon atom per molecule). Alternatively, the silyl hydride may be oligomeric or polymeric. A polymeric silyl hydride may be linear, branched, or resinous. For example, the silyl hydride may be B2) a polyorganohydrogensiloxane. Alternatively, the silyl hydride may be B3) an organic polymer functionalized with a moiety comprising SiH.

[0030] B1) Silane

[0031] The starting material B1) is of formula H k S i 5 (4-k) Silane, where each R 5 are independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, and subscript k is 1 to 3, alternatively 1 or 2, and alternatively 1. For R 5 Examples of suitable monovalent hydrocarbon groups include, but are not limited to, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and their branched chain isomers); cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, butenyl, and hexenyl; and aryl groups such as phenyl, tolyl, xylyl, naphthyl, benzyl, 1-phenylethyl, and 2-phenylethyl. 5Examples of monovalent halogenated hydrocarbon groups include, but are not limited to, chlorinated alkyl groups such as chloromethyl groups 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, 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 It may be a monovalent hydrocarbon group, alternatively an alkyl group or an aryl group. Alternatively, each R 5 It may be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms. 5 Alternatively, the starting material B1) may be of the formula HSiR 5 3 silane, wherein each R 5 It is an alkyl group of 1 to 6 carbon atoms.

[0032] Examples of suitable silanes of starting material B1) are known in the art and are commercially available. Suitable silanes include triethylsilane, dimethylethylsilane, diethylmethylsilane, dimethylisopropylsilane, dimethyltert-butylsilane, triisopropylsilane, chloromethyldimethylsilane, tripropylsilane, tributylsilane, triisobutylsilane, trihexylsilane, trioctylsilane, cyclohexyldimethylsilane, dimethylphenylsilane, diphenylmethylsilane, triphenylsilane, phenylsilane, undecylbromosilane, 2-chloroethylsilane, dodecylsilane, n-octadecylsilane, and (tridecafluoro-1,1,2,2-tetrahydrooctyl)silane, which are available from Sigma-Aldrich Inc. of St. Louis Missouri, USA or Gelest Inc. of Morrisville, Pennsylvania, USA.

[0033] B2) Polyorganohydrogensiloxane

[0034] When starting material B2) a polyorganohydrogensiloxane is used, 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 may be located at the terminal, pendant or both terminal and pendant positions.

[0035] The polyorganohydrogensiloxane may include a 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 In the above formula, each R 4 are independently selected monovalent hydrocarbon groups free of aliphatic unsaturation. 4 Examples of suitable monovalent hydrocarbon groups include, but are not limited to, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and their branched chain isomers); cycloalkyl groups such as cyclopentyl and cyclohexyl; and aryl groups such as phenyl, tolyl, xylyl, naphthyl, benzyl, 1-phenylethyl, and 2-phenylethyl. Alternatively, each R 4 It may be an alkyl group or a cycloalkyl group. 4 It may be an alkyl group, such as methyl.

[0036] When the polyorganohydrogensiloxane is linear, that is, polydiorganohydrogensiloxane, the polydiorganohydrogensiloxane may have a 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 As described above, and the values ​​of the subscripts g, h, i and j are such that g≥0, h≥0, the average value of the quantity (g+h) is 2, i≥0, j≥0, and the quantity (g+j)≥1, and the quantity (i+j) is in the range of 0 to 1000.

[0037] Alternatively, the polydiorganohydrogensiloxane may have the formula where the subscript m is 0 or 1, and each R 6 Independently selected from the group consisting of: H and R 4 , the prerequisite is that at least one R 6 It's a hydrogen atom.

[0038] Examples of suitable polyorganohydrogensiloxanes are:

[0039] 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),

[0040] viii) polymethylhydrogensiloxane terminated with bistrimethylsilyloxy groups, ix) essentially composed of H(CH3)2SiO 1 / 2 Unit and SiO 4 / 2 A resin having a unit composition, and a combination of two or more of x)i) to ix).

[0041] Methods for preparing linear and branched polyorganohydrogensiloxanes suitable for use as starting material B2) (e.g., hydrolysis and condensation of organohalosilanes) are well known in the art, as exemplified in U.S. Pat. Nos. 5,310,843; 4,370,358; 4,707,531; and 4,329,273. Polyorganohydrogensiloxanes are also commercially available, such as those available from Gallester Corporation under the following trade names: DMS-HM15, DMS-H03, DMS-H25, DMS-H31, and DMS-H41.

[0042] B3) Silyl-functional polyolefin

[0043] The starting material B3) has a silicon-bonded hydrogen functional group of the formula (B3-1): A polyolefin, wherein each R 1 is an independently selected monovalent hydrocarbon group and each subscript a is independently 1 or 2. 1 Suitable monovalent hydrocarbon groups for may have 1 to 20 carbon atoms, alternatively 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms, alternatively 1 to 4 carbon atoms, and alternatively 1 to 2 carbon atoms. Alternatively, for R 1The monovalent hydrocarbon group of can be selected from the group consisting of: alkyl group, alkenyl group and aryl group; alternatively alkyl and aryl; and alternatively alkyl. Examples of alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl and / or tert-pentyl), hexyl, heptyl, octyl, nonyl and decyl, and branched saturated monovalent hydrocarbon groups with 6 or more carbon atoms, including cycloalkyl groups such as cyclopentyl and cyclohexyl. Alkenyl groups are exemplified by, but not limited to, vinyl, allyl, butenyl (including n-butenyl, isobutenyl and / or tert-butenyl) and hexenyl (including their straight chain and branched chain isomers). Aryl groups are exemplified by cyclopentadienyl, phenyl, tolyl, xylyl, anthracenyl, benzyl, 1-phenylethyl, 2-phenylethyl, and naphthyl. Monocyclic aryl groups may have 5 to 9 carbon atoms, or 6 to 7 carbon atoms, and or 5 to 6 carbon atoms. Polycyclic aryl groups may have 10 to 17 carbon atoms, or 10 to 14 carbon atoms, and or 12 to 14 carbon atoms. Alternatively, each R 1 may be independently selected from the group consisting of alkyl and aryl, alternatively methyl and phenyl. Alternatively, each R 1 It may be methyl.

[0044] The starting material B3) silyl-functional polyolefin may have silyl groups of formula (B3-1) in the pendant position. For example, the silyl-functional polyolefin having pendant silyl groups may be a polyolefin comprising the unit formula (B3-2):

[0045] SiH functionalized polyolefin copolymer, wherein R 1 and subscript a as described above.

[0046] Each D in the unit formula (B3-2) 1 is independently a divalent hydrocarbon group of 2 to 50 carbon atoms. 1 Examples of divalent hydrocarbon groups are alkylene groups such as ethylene, propylene, butylene, hexylene or octylene; arylene groups such as phenylene, or alkylenearyl groups such as:

[0047] Alternatively, each D 1 is an alkylene group such as ethylene, propylene or octylene.

[0048] In unit formula (B3-2), each R 25 are independently H, a monovalent hydrocarbon group of 1 to 18 carbon atoms, or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms. 25 Examples of monovalent hydrocarbon groups are as described herein for R having 1 to 18 carbon atoms.1 Those described. Suitable monovalent halogenated hydrocarbon groups include haloalkyl groups, halocyclic groups, and haloalkenyl groups. Haloalkyl groups include fluoroalkyl groups such as 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; and chloroalkyl groups such as chloromethyl, 3-chloropropyl, 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl. Haloalkenyl groups include chloroallyl. Alternatively, each R 25 can be an alkyl group having 1 to 6 carbon atoms. Alternatively, each R 25 can be H.

[0049] In the unit type (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 can have values such that the amount M / (M + N) satisfies 0.01 mol% ≤ M / (M + N) ≤ 10 mol%. Alternatively, the subscripts M and N can have values sufficient to provide a copolymer having a Mn of 1,000 to 500,000.

[0050] This SiH-functional polyolefin can also include R 21 capping groups at each end. Each R 21 can 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, vinylene, or vinylidene functional group). Examples of such SiH-functional polyolefins (silyl-functional olefin interpolymers) and their preparation methods are disclosed, for example, in U.S. Patent 6,624,254 to Arriola et al.

[0051] Alternatively, B3) The silyl-functional polyolefin can include a silyl-capped polyolefin having 1 to 2 terminal silyl groups of formula (B3-1) per molecule. The silyl-capped polyolefin can have the unit type (B3-3):

[0052] where the subscripts a and R 1 are as described above, the subscript f is from 0 to 1, the relative values of the subscripts t and u are such that 0 < t ≤ 1, 0 ≤ u ≤ 1, the subscript g is 1 or greater, each R et represents an ethylene unit, and each R O represents an olefin unit other than ethylene. RO The alkylene group of the present invention can be alkylene or alkylene. ...

[0053] Alternatively, the silyl-terminated polyolefin may have the unit formula (B3-4): The subscripts a, f, g, t, and u, as well as R 1 As mentioned above. Each R 7 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. 7 The monovalent hydrocarbon group of may be an alkyl, alkenyl or aryl group; alternatively an alkyl group. Alternatively, R 7 may be an alkyl group having 2 to 12 carbon atoms and alternatively 2 to 6 carbon atoms. Alternatively, each R 7 It is a hexyl group.

[0054] The silyl-terminated polyolefin may have one terminal silyl group per molecule (i.e., where the subscript f=1). Examples of such silyl-terminated polyolefins having a silyl group at one end of the polymer chain include dimethyl, hydrosilyl-terminated polyethylene; dimethyl-hydrosilyl-terminated poly(ethylene / octene) copolymer; methyl-dihydrosilyl-terminated polyethylene; methyl-dihydrosilyl-terminated poly(ethylene / octene) copolymer; diphenyl-hydrosilyl-terminated polyethylene; diphenyl-hydrosilyl-terminated poly(ethylene / octene) copolymer; phenyl-dihydrosilyl-terminated polyethylene; phenyl-dihydrosilyl-terminated poly(ethylene / octene) copolymer; chlorophenylhydrosilyl-terminated polyethylene; or chlorophenylhydrosilyl-terminated poly(ethylene / octene) copolymer. This silyl-terminated polyolefin can be prepared by the method described in PCT Publication WO2019 / 082992 corresponding to U.S. patent application serial number 62 / 644635 filed on March 19, 2018, and PCT Publication WO2019 / 182986 corresponding to U.S. patent application serial number 62 / 644624 filed on March 19, 2018, all of which are hereby incorporated by reference.

[0055] Alternatively, the starting material B3) silyl-terminated polyolefin may have two silyl terminal groups per molecule (i.e., in formula (B3-3) and formula (B3-4), where subscript f=0, the silyl-terminated polyolefin is telechelic). Such telechelic silyl-terminated polyolefins may be prepared by methods such as those disclosed in PCT publication WO2019 / 182993 corresponding to U.S. patent application serial number 62 / 644808 filed on March 19, 2018, which is hereby incorporated by reference.

[0056] The starting material B3) may be a silyl hydride or may comprise two or more silyl hydrides differing in at least one property. For example, the starting material B3) may be a silyl functional polyolefin or may comprise two or more silyl functional polyolefins differing in at least one of the following properties: structure, viscosity, average molecular weight, olefin block and sequence.

[0057] C) Water

[0058] Starting material C) water is generally not limited and can be used undiluted (i.e., without any solvent) and / or in pure form (i.e., free of or substantially free of minerals and / or other impurities). For example, water C) can be treated or untreated before use in the methods described above. Examples of methods that can be used to purify water include distillation, filtration, deionization, and combinations of two or more thereof, such that the water can be deionized, distilled, and / or filtered. Alternatively, the water can be untreated (e.g., tap water provided by a city water system, or well water, which can be used without further purification).

[0059] Water may be used in any amount which will be selected by one skilled in the art based on factors such as the particular catalyst selected for starting material A), the reaction parameters employed and the scale of the reaction (e.g., total amount and SiH content of starting material B).

[0060] D) Solvent

[0061] Starting material D) is an optional solvent, which can be used to promote the combination of starting materials. Solvents used herein are those that contribute to the fluidization of starting materials but do not react with any of these starting materials substantially. Solvents can be selected based on the solubility of starting materials and the volatility of solvents. Solubility refers to that the solvent is sufficient to dissolve and / or disperse the starting materials. Volatility refers to the vapor pressure of the solvent. For example, starting material A) fluorinated triaryl borane Lewis acid can be dissolved in a solvent before step 1). Alternatively, for example, when starting material B) is viscous, elastomeric or resinous, starting material B) can be dissolved in a solvent. The solvent can be used in any amount, and the amount will be selected by those skilled in the art according to various factors, such as starting material B) selection and starting material A) solubility therein.

[0062] 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 comprising two or more solvents may be used herein.

[0063] The amount of solvent may depend on a variety of factors, including the type of solvent selected and the amount and type of other starting materials selected. However, based on the combined weight of starting material A) and starting material B), the amount of solvent may be in the range of 0.1% to 99%, alternatively 2% to 50%.

[0064] Starting material E) Neutralizing agent

[0065] Starting material E) is a neutralizing agent, which can be optionally used to neutralize starting material A after product formation. Alumina, triphenylamine, triethylamine, triphenylphosphine and phenylacetylene are suitable neutralizing agents. Neutralizing agents are known in the art and can be commercially obtained, for example, from Millipore Sigma, St. Louis, Missouri, USA. The amount of the neutralizing agent depends on various factors including the amount of starting material A), however, starting material E) can be present in an amount sufficient to provide a weight ratio (E: A ratio) of neutralizing agent to fluorinated triaryl borane Lewis acid of 100: 1 to 1: 1000, alternatively 1: 1 to 1000: 1, and alternatively 100: 1 to 1: 1. Alternatively, when the neutralizing agent is triphenylphosphine or phenylacetylene, the E: A ratio can be 1: 1 to 20: 1. Alternatively, when the neutralizing agent is alumina, the E:A ratio may be from 100:1 to 1000:1.

[0066] How to use

[0067] The compositions and methods described herein can be used to prepare siloxanes, siloxane-organic hybrid copolymers, intermediates and / or branched siloxane networks. Without being bound by theory, it is believed that the compositions and methods described herein can be used as curing systems for various formulations and applications. When starting material A) and starting material B) are combined and stored before use, the composition provides the benefit of storage stability.

[0068] Example

[0069] These examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention described in the claims.The starting materials described in Table 1 and Reference Examples 1 and 2 were used in the examples herein.

[0070] Table 1 - Starting materials

[0071]

[0072]

[0073] Reference Example 1 - General Procedure

[0074] Unless otherwise stated, all experimental procedures and manipulations of chemicals were performed in a nitrogen-purged glove box or Schlenk line. All bulk reaction solvents (toluene, diethyl ether, hexane, tetrahydrofuran (THF)) were dried over alumina and Q5 reactive scavenger columns. All other solvents were purchased from Aldrich anhydrous grade and activated with Molecular sieves were stored. NMR solvents (CDCl3, CD2Cl2, and C6D6) were obtained from Cambridge Isotope Laboratories, Inc. and activated Molecular sieve drying or, in the case of C6D6, Na / K alloy drying. 1-Bromo-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. Prior to use, n-Butyl lithium (hexane solution) was titrated using 1.00 M decanol in toluene with 1,10-phenanthroline as an indicator. 1

[0075] Multinuclear NMR spectra were collected on one of the following instruments: 1 H. 13 C.19 F. 29 4. 11 B): Varian MR-400 or Varian VNMRS-500. 11 B NMR spectra were collected only on a Varian VNMRS-500. 1 H and 13 C NMR chemical shifts are expressed in parts per million relative to the residual solvent peak: 1 H- is 5.32 ppm for CD2Cl2, 7.15 ppm for C6D6, and 7.25 ppm for CDCl3; 13 C- is 54.00 ppm for CD2Cl2, 128.00 ppm for C6D6, and 77.00 ppm for CDCl3. 11 BNMR chemical shifts were externally referenced to BF3(Et2O) (0 ppm), 19 F NMR chemical shifts were externally referenced to CFCl3 (0 ppm). Except when using dry ice or ice as the only means of cooling, subambient reaction temperatures were measured using an Extech Instruments EasyView with fine JKEM sensor PTFE wire K36INJ. TM 10 Dual K model EA 10 thermometer for measurement.

[0076] Reference Example 2 - Synthesis Procedure - Preparation of Starting Materials

[0077] The preparation of lithium (diethyl etherate) (3,5-bis(trifluoromethyl)phenyl) triisopropoxyborate was carried out as follows:

[0078]

[0079] 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-butyl lithium (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 diethyl ether (20 mL) was slowly added. The reaction mixture was stirred at -78°C for 1 hour, then allowed to warm to ambient temperature and stirred for 1 hour to give a slightly turbid solution. The reaction mixture was filtered, and the volatiles were removed under reduced pressure to give a solid. The solid was ground with hexane, filtered, and the volatiles were removed under reduced pressure to give a product as a colorless powder. Yield: 23.16 g, 94.53%. The compound was initially isolated as its ether adduct.

[0080] 1 H NMR (500MHz, THF-d8) δ8.15 (s, 2H), 7.57 (s, 1H), 3.79 (p, J = 6.1 Hz, 3H), 0.95 (d, J = 6.1 Hz, 18H). 13 C NMR(126MHz,THF-d8)δ159.12,134.71,128.90(q,J=31.3Hz),125.91(q,J=271.8Hz),118.70,6 7.41 (dtd, J = 44.2, 22.2, 2.9Hz), 61.67, 26.53 (d, J = 17.7Hz), 25.28 (dtd, J = 40.4, 20.1, 3.0Hz). 19 F NMR(470MHz,THF-d8)δ-63.02. 11 B NMR (160 MHz, THF-d8) δ 3.84.

[0081] The preparation of (3,5-bis(trifluoromethyl)phenyl)diisopropoxyborane was carried out as follows:

[0082]

[0083] 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, 2M in diethyl ether, 24.6 mmol) and a precipitate formed immediately. The reaction mixture was stirred for two 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 give the product as an oil. Yield: 5.10 g, 76.1%.

[0084] 1 H 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 C 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 F NMR (470 MHz, chloroform-d) δ -63.34.11 B NMR (160 MHz, chloroform-d) δ 26.66.

[0085] The preparation of lithium (diethyl etherate) bis(3,5-bis(trifluoromethyl)phenyl)diisopropoxyborane was carried out as follows:

[0086]

[0087] To a cold (-78°C, CO2(s) bath) solution of 1-bromo-3,5-bis(trifluoromethyl)benzene (4.26 g, 14.5 mmol) in diethyl ether (200 mL) was added n-butyl lithium (5.30 mL, 2.61 M in hexane, 60.0 mmol) 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 diethyl ether (15 mL) was slowly added. The reaction mixture was stirred at -78°C for 1 hour (some solids were visible), then allowed to warm to ambient temperature and stirred overnight to give a clear solution. The volatiles were removed under reduced pressure to give a crystalline solid. The solid was dissolved in hexane, and the solution was filtered and placed in a 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. Material yield: 8.23 ​​g, 93.5%.

[0088] 1 H 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 C 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 F NMR (376 MHz, chloroform-d) δ -63.05. 11 B NMR (160 MHz, chloroform-d) δ 5.12.

[0089] The preparation of bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane was carried out as follows:

[0090]

[0091] 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 hydrogen chloride solution (5.5 mL, 2M in diethyl ether, 11 mmol) and a precipitate formed immediately. The reaction mixture was stirred for one hour and the volatiles were removed under reduced pressure. The residue was extracted with hexanes, 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 was present).

[0092] 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.

[0093] Synthesis procedure - preparation of catalyst

[0094] Catalyst Sample C1, tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct, was prepared as follows:

[0095] Preparation of lithium isopropoxy tris(3,5-bis(trifluoromethyl)phenyl)borate

[0096]

[0097] n-Butyl lithium (5.00 mL, 2.5 M in hexane, 12.7 mmol) was slowly added dropwise to a cold (-78°C, CO2(s) bath) solution of 1-bromo-3,5-bis(trifluoromethyl)benzene (3.76 g, 12.8 mmol) in diethyl ether (150 mL). The reaction mixture was stirred at -78°C for 1 hour. Isopropoxy-bis(3,5-bis(trifluoromethyl)phenyl)borane (6.29 g, 12.7 mmol) in diethyl ether (10 mL) was slowly added. The reaction mixture was stirred overnight while warming to ambient temperature to give a clear, very pale yellow solution. The volatiles were removed under reduced pressure to give a crystalline solid. The solid was dissolved in minimal boiling diethyl ether and the solution was placed in a freezer. After cooling overnight, the supernatant was decanted from the crystals that had formed, and the crystals were dried under reduced pressure to give 6.74 g. The supernatant solution was concentrated and cooled in the freezer overnight to give a second crop of crystalline material (1.54 g).Total yield: 8.28 g, 75.6%.

[0098] 1 H NMR (400 MHz, benzene-d6) δ 8.09 (s, 6H), 7.74 (s, 3H), 3.71 (p, J = 6.1 Hz, 1H), 2.97 (q, J = 7.0 Hz, 10H), 0.70 (t, J = 7.1 Hz, 15H), 0.67 (d, J = 6.2 Hz, 6H). 13 C NMR (101 MHz, benzene-d6) δ 157.09, 133.79, 130.75 (q, J = 32.0 Hz), 124.71 (q, J = 272.8 Hz), 119.91 (p, J = 4.2 Hz), 65.91, 65.00, 25.47, 14.11. 19 F NMR (376 MHz, benzene-d6) δ -62.76. 11 B NMR (160 MHz, benzene-d6) δ 1.56.

[0099] Preparation of tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct

[0100]

[0101] To a solution of lithium isopropoxytris(3,5-bis(trifluoromethyl)phenyl)borate (6.700 g, 7.75 mmol) in diethyl ether (100 mL) was added trimethylsilyl chloride (2.0 mL, 1.71 g, 15.8 mmol). The reaction mixture was stirred over the weekend. The reaction mixture was filtered and the volatiles were removed under reduced pressure to give the product as a colorless solid, 4.80 g, 95.2%.

[0102] 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%.

[0103] THF adduct: 1 H NMR (400MHz, benzene-d6) δ7.80-7.78(m,6H),7.72(dq,J=1.8,0.9Hz,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.

[0104] Catalyst Sample C2, bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct, was prepared as follows.

[0105] Preparation of Bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane

[0106]

[0107] n-Butyl lithium (4.70 mL, 2.535 M in hexane, 11.9 mmol) was slowly added dropwise to a cold (-78 ° C, CO2 (s) / acetone bath) solution of 1-bromo-4-trifluorotoluene (2.750 g, 12.22 mmol) in diethyl ether (200 mL). The reaction mixture was stirred at -78 ° C for 3 hours. Isopropoxybis(3,5-bis(trifluoromethyl)phenyl)borane (5.910 g, 11.91 mmol) in diethyl ether (15 mL) was slowly added. The reaction mixture was warmed to ambient temperature while stirring overnight to obtain a clear yellow solution with trace amounts of precipitation. The solvent was removed under reduced pressure to obtain a viscous yellow oil. The oil was rapidly stirred overnight with hexane (100 mL) (producing some turbidity). The hexane layer was decanted, filtered, and volatiles were removed under reduced pressure. The oil layer was extracted with hexane again and the process was repeated several times. Discard a small amount of undissolved oil. Remove volatiles from the filtrate under reduced pressure to obtain a yellow oil. The oil is dissolved in diethyl ether (100mL) and trimethylchlorosilane (TMSCl, 1.5g, 13.8mmol) is added. A large amount of precipitation is formed in 30 minutes. The reaction mixture is stirred overnight. Filter the reaction mixture, and remove volatiles under reduced pressure to obtain a pasty beige sludge. NMR spectrum shows almost complete reaction. The product is dissolved in ether and more TMSCl (0.4mL) is added. After stirring for several hours, remove volatiles under reduced pressure. Residue is extracted with benzene, filtered, and remove volatiles under reduced pressure to obtain a pasty solid. 1 The H NMR spectrum still shows some isopropyl groups and some ether. The residue was dissolved in ether, a small amount of TMSCl (0.2 mL) was added, and the reaction mixture was stirred for several hours. A few milliliters of THF were added, and the volatiles were removed under reduced pressure. The product was extracted with benzene, filtered, and the volatiles were removed under reduced pressure to obtain the product as a white solid (5.370 g, 68.90%).

[0108] NMR spectrum of borane-THF complex: 1 H NMR (400MHz, benzene-d6) δ7.83 (s, 4H), 7.78 (tq, J=1.7, 0.8Hz, 2H), 7.41 (dq, J=7.4, 0.8Hz, 2H), 7.07 (dq, J = 7.5, 0.9Hz, 2H), 3.04-2.96 (m, 4H), 0.70-0.62 (m, 4H). 13C NMR (126MHz, benzene-d6) δ149.08, 148.88, 134.18, 133.62 (d, J = 3.8Hz), 131.11 (q, J = 32.4Hz), 129.94 (q, J = 32.1Hz) ,125.06(d,J=272.1Hz), 124.92(q,J=3.8Hz), 124.34(q,J=272.7Hz), 121.22(dt,J=8.0,4.0Hz), 73.53,24.10. 19 F NMR (376 MHz, benzene-d6) δ -62.56 (s, 3F), -62.78 (s, 12F). 11 B NMR (160 MHz, benzene-d6) δ 18.54.

[0109] Catalyst Sample C3, bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct, was prepared as follows:

[0110] Preparation of Lithium Bis(Diethyl Ether)Bis(3,5-Bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)-Isopropoxyborate

[0111]

[0112] In the glove box purged by N2, 2.06g (9.78mmol) 1-bromo-2,4,6-trifluorobenzene is combined with 80mL diethyl ether in a 250mL Schleck flask. A polytetrafluoroethylene-coated stirring rod is added to the colorless solution, and the flask is sealed with a rubber septum before being taken out from the glove box. In a fume hood, the flask is connected to a nitrogen line, and is placed in a dry ice / acetone bath (-78°C) and frozen for 20 minutes. A solution of 2.5M n-butyl lithium in hexane (4.3mL, 10.8mmol) is added to the cold solution via a syringe. The reaction mixture is stirred at -78°C for 1 hour. A solution of 4.85g bis (3,5-bis (trifluoromethyl) phenyl) isopropoxy borane in 20mL diethyl ether is prepared in a glove box, and drawn into a syringe. The solution is injected into a flask containing a cold aryl lithium solution at -78°C, and the mixture is stirred at this temperature for half an hour. Remove the dry ice / acetone bath, and allow the reaction mixture to slowly warm to room temperature while stirring overnight. The next morning, all volatiles were removed under vacuum to obtain a sticky yellow solid. The flask was returned to the glove box, and the sticky yellow material was extracted with 1) 80 mL pentane, 2) 80 mL hexane and 3) 60 mL 50 / 50 ether / hexane mixture. All three solutions were placed in a glove box freezer overnight (-40 ° C) and white crystalline material was precipitated from the solution. The crystalline material was collected by filtration, washed with cold pentane (-40 ° C), and dried under vacuum for 1 hour. Total yield: 5.29 g (impure, about 5.5 mmol desired lithium salt, 56%). It should be noted that no pure material was obtained; the lithium salt was contaminated by isopropoxyborane starting material (12%-22% contaminated, depending on the solid material batch collected). It was decided to proceed to the next step in the reaction without any further purification of the separated material.

[0113] 1 H NMR (400 MHz, benzene-d6) δ8.26 (s, 4H, o-ArCH), 7.80 (s, 2H, p-ArCH), 6.22-6.07 (m, 2H, o-ArCH), 3.68 (hept, J=5.8 Hz, 1H, CH(CH3)2), 3.07 (q, J=7.1 Hz, 8H, OCH2), 0.81 (t, J=7.1 Hz, 12H, OCH2CH3), 0.67 (d, J=6.2 Hz, 6H, CH(CH3)2). 13C NMR (101 MHz, benzene-d6) δ 166.2 (ddd, J = 231.3, 22.4, 14.0 Hz, ArC), 162.3 (dt, J = 247.1, 20.2 Hz, ArC), 159.5 (br s, ArC), 157.3 (br s,ArC), 133.8(s,o-ArCH), 130.7(q, J=31.9Hz,ArC-CF3), 125.5(q, J=272.4Hz,CF3), 119.9(p, J=4.0Hz,p-ArCH), 101.0(ddd, J=36.6,24.0,3.7Hz,m-ArCH), 65.9(s,OCH(CH3)2), 65.8(s,OCH2CH3), 25.7(s,OCH(CH3)2), 14.7(s,OCH2CH3). 19 F NMR (376 MHz, benzene-d6) δ -62.7 (s, 12F, CF3), -104.4 (br s, 2F, o-ArF), -112.3 (m, 1F, p-ArF).

[0114] Preparation of Bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoro)borane

[0115]

[0116] In a N2 purged glove box, 3.30 g (78% purity, 3.29 mmol) of lithium borate salt was dissolved in 60 mL of diethyl ether to form a colorless solution (Note: borane lithium salt was contaminated with 22% bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane). Trimethylsilyl chloride (1.0 mL, 7.9 mmol) was added to the solution under stirring at room temperature. There was no sign of immediate reaction. The mixture was stirred at room temperature overnight. The next morning, a large amount of LiCl precipitate formed in the flask. An aliquot of the reaction mixture was taken out and the mixture was filtered by 19 F NMR spectroscopy is to confirm that the reaction is complete. The reaction mixture is filtered through diatomaceous earth to remove LiCl, and the filtrate is evacuated to dryness. The resulting sticky white solid is extracted with 80-90mL hexane and filtered again. The hexane solution is placed in a glove box freezer overnight (-40°C), during which time a white microcrystalline solid is precipitated. The solid is collected by filtration, washed with 5-10mL cold pentane (-40°C), and dried under vacuum for 1 hour. Multinuclear NMR spectroscopy confirms that the desired substance in pure form has been formed. Yield: 0.992g, 1.75mmol, 53.2%.

[0117] 1H NMR (400 MHz, benzene-d6) δ 7.88 (s, 6H, ArCH on the CF3-substituted ring), 6.03 (m, 2H, ArCH on the 2,4,6-trifluorobenzene ring). 13 C NMR (101 MHz, benzene-d6) δ 167.4 (dt, J = 257.6, 16.2 Hz, p-ArCF), 166.2 (dt, J = 253.5, 15.2 Hz, o-ArCF), 142.8 (br s, ArC), 137.5 (d, J = 3.0 Hz, o-ArCH), 132.1 (q, J = 33.4 Hz, ArC-CF3), 126.9 (pent, J = 4.0 Hz, p-ArCH), 124.1 (q, J = 273.0 Hz, CF3), 112.6 (br s, ArC), 101.6 (ddd, J = 29.0, 24.9, 3.7 Hz, m-ArCH). 19 F NMR (376 MHz, benzene-d6) δ -63.1 (s, 12F, CF3), -92.4 (m, 2F, o-ArCF), -98.5 (s, 1F, p-ArCF). 11 B NMR (160 MHz, benzene-d6) δ 62.9 (broad s).

[0118] Preparation of THF adduct of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoro)borane

[0119]

[0120] In a N2 purged glove box, 0.992 g (1.75 mmol) of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane was weighed into a 110 mL glass jar and dissolved in 50 mL of THF. The THF was removed under vacuum with stirring to produce a white solid. The solid was triturated with 40 mL of pentane to help remove any uncoordinated THF. The white solid was characterized by multinuclear NMR spectroscopy as the mono-THF adduct of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoro-phenyl)borane. Yield: 0.969 g, 1.51 mmol, 86.3%.

[0121] 1 H NMR (400 MHz, benzene-d6) δ 7.96 (s, 4H, o-ArCH), 7.79 (s, 2H, p-ArCH), 6.16 (t, J=8.0 Hz, 2H, m-ArCH), 3.10 (m, 4H, OCH2), 0.79 (m, 4H, CH2). 13C NMR (101 MHz, benzene-d6) δ 165.3 (ddd, J = 245.4, 17.7, 14.3 Hz, o-ArCF), 163.9 (dd, J = 249.5, 16.2 Hz, p-ArCF), 148.4 (brs, ArC), 134.0 (s, o-ArCH), 131.4 (q, J = 32.4 Hz, ArC-CF3), 121.8 (m, p-ArCH), 124.8 (q, J = 272.7 Hz, CF3), 101.3 (ddd, J = 32.8, 24.2, 3.2 Hz, m-ArCH), 72.6 (s, OCH2), 24.8 (s, CH2). 19 FNMR (376 MHz, benzene-d6) δ -62.8 (s, 12F, CF3), -96.9 (s, 2F, o-ArCF), -108.5 (s, 1F, p-ArCF). 11 B NMR (160 MHz, benzene-d6) δ 13.2 (broad s).

[0122] Catalyst Sample C4, bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)THF adduct, was prepared as follows:

[0123] Preparation of Lithium Bis(Diethyl Ether)Bis(3,5-Bis(Trifluoromethyl)phenyl)(2,6-Difluorophenyl)-Isopropoxyborate

[0124]

[0125] n-Butyl lithium (3.00 mL, 2.48 M in hexane, 7.44 mmol) was slowly added dropwise to a cold (-78 ° C, CO2 (s) bath) solution of 1-bromo-2,6-difluorobenzene (1.46 g, 7.56 mmol) in diethyl ether (100 mL). The reaction mixture was stirred at -78 ° C for 1 hour, and then a solution of bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane (3.69 g, 7.44 mmol) in diethyl ether (10 mL) was slowly added. A precipitate was formed while the reaction mixture was warmed to ambient temperature. By the time the reaction mixture had reached room temperature, the precipitate dissolved to give a clear solution, which was stirred for several hours. The solution was filtered and the volatiles were removed under reduced pressure to give a crystalline solid. The solid was dissolved in minimal boiling diethyl ether, and the solution was placed in a glove box freezer (-33 ° C). After cooling overnight, the supernatant was decanted from the crystals that had formed. The crystals were dried under reduced pressure. Yield: 6.85 g, 88.4%.

[0126] 1H NMR (400MHz, benzene-d6) δ8.31 (s, 4H), 7.77 (tt, J=2.0, 0.9Hz, 2H), 6.60 (dq, J=8.8, 7.5Hz, 1H), 6.47-6.41 (m, 2H) ,3.71(hept,J=6.2Hz,1H),3.05(qd,J=7.1,0.7Hz,8H),0.82(td,J=7.1,0.6Hz,12H),0.68(d,J=6.2Hz,6H). 13 C NMR (126MHz, benzene-d6) δ164.45(dd,J=249.6,11.3Hz),142.11,137.21,136.78(t,J=3.8Hz),135.51(t,J=10.8Hz),1 31.28(q,J=33.3Hz),126.10(p,J=3.8Hz),123.30(q,J=273.1Hz),111.72-111.40(m),73.82,65.57,15.11,2.57. 19 F NMR (376 MHz, benzene-d6) δ -62.64, -106.66. 11 B NMR (160 MHz, benzene-d6) δ 0.68 (s).

[0127] Preparation of THF adduct of bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane

[0128]

[0129] Lithium bis(diethyl etherate)bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)isopropoxyborate (5.85 g, 10.6 mmol) was dissolved in diethyl ether (150 mL) and trimethylsilyl chloride (3.00 mL, 23.6 mmol) was added to the solution at ambient temperature. A precipitate began to form within 15 minutes. The reaction mixture was allowed to stir over the weekend. By Monday, the volatiles had evaporated (non-sealed container). The colorless solid was extracted with diethyl ether and filtered. The volatiles were removed under reduced pressure to give the product as a colorless solid, 4.98 g. The NMR spectrum showed pure borane, but only about 86% of the desired diethyl ether for the monoetherate complex. The product was dissolved in diethyl ether to give a turbid solution. THF (6 mL) was added and the solution became crystalline and transparent. The volatiles were removed under reduced pressure to give a glassy solid. The residue was extracted with benzene, filtered, and the volatiles were removed under reduced pressure to give a white solid. Yield: 4.63 g, 69.9%.

[0130] 1H NMR(400MHz, benzene-d6)δ8.02(d,J=1.8Hz,2H),7.77(dq,J=1.9,0.9Hz,1H),6.7 1-6.60(m,0H),6.48(t,J=8.4Hz,1H),3.17-3.09(m,2H),0.77-0.68(m,2H). 13 C NMR (101 MHz, benzene-d6) δ 164.82 (dd, J = 243.3, 14.1 Hz), 147.95, 133.82, 133.30, 130.91 (d, J = 32.4 Hz), 124.41 (q, J = 272.8 Hz), 121.40 (q, J = 3.9 Hz), 112.57-111.60 (m), 73.58, 24.03 (d, J = 3.3 Hz). 19 F NMR (376 MHz, benzene-d6) δ -62.80, -99.69 (t, J = 7.5 Hz). 11 B NMR (160 MHz, benzene-d6) δ 12.2 (s).

[0131] Catalyst Sample C5, bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane, was prepared as follows:

[0132] Preparation of Lithium Isopropoxybis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0133]

[0134] n-Butyl lithium (4.00 mL, 2.535 M in hexane, 10.14 mmol) was slowly added to a cold (-78 ° C, CO2 (s) bath) solution of 1-bromo-2,5-bis (trifluoromethyl) benzene (3.00 g, 10.24 mmol) in diethyl ether (200 mL). The reaction mixture was stirred at -78 ° C for 1 hour. Isopropoxy-bis (3,5-bis (trifluoromethyl) phenyl) borane (5.036 g, 10.15 mmol) in diethyl ether (18 mL) was slowly added. The reaction mixture was stirred at -78 ° C for several hours. The solution was warmed to ambient temperature while stirring overnight to give a pale yellow clear solution. Volatiles were removed from the reaction mixture to give a yellow oil. The oil was extracted with benzene. There was no insoluble matter. Volatiles were removed from the reaction mixture to give a yellow oil. The yield was 7.88 g, 98.3%.

[0135] 1H NMR (400MHz, benzene-d6) δ8.06(s,1H),8.00(s,4H),7.70(dt,J=1.8,0.9Hz,2H),7.40(d,J=8.3Hz,1H),7.19(d,J =8.4Hz, 1H), 3.79 (hept, J = 6.1Hz, 1H), 2.78 (q, J = 7.1Hz, 4H), 0.73 (d, J = 6.1Hz, 6H), 0.54 (t, J = 7.1Hz, 6H). 13 C NMR (101MHz, benzene-d6) δ158.31, 153.97, 135.44 (q, J = 3.7Hz), 135.23, 133.5 5(t,J=4.1Hz),133.25,133.18,132.37(d,J=97.8Hz),130.92(q,J=32.0H z),127.80(q,J=273.9Hz),124.92(q,J=272.5Hz),124.66(q,J=272.8Hz ), 123.86 (q, J = 3.8Hz), 119.86 (p, J = 3.9Hz), 66.24, 66.17, 25.60, 13.94. 19 F NMR (376 MHz, benzene-d6) δ -55.30--55.51 (m), -62.82, -63.61. 11 B NMR (160 MHz, benzene-d6) δ 2.16.

[0136] Preparation of Bis(3,5-Bis(trifluoromethyl)phenyl)(2,5-Bis(trifluoromethyl)phenyl)borane

[0137]

[0138] Lithium (diethyl ether) isopropoxy-bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate (7.88 g, 9.97 mmol) was dissolved in diethyl ether (150 mL). Trimethylsilyl chloride (2.6 mL, 20.5 mmol) was added. The reaction mixture was stirred overnight to give a yellow solution with a colorless precipitate. All volatiles were removed under reduced pressure. The residue was extracted with hexane (100 ml). The mixture was filtered and the volatiles were concentrated under reduced pressure. The solution was cooled in a freezer (-33 ° C) overnight. The reaction mixture was filtered and the precipitate was dried under reduced pressure to give a white powder. Yield: 6.0182 g, 92.84%.

[0139] Compounds without THF: 1H NMR (400 MHz, benzene-d6) δ 7.87 (s, 2H), 7.85 (s, 4H), 7.29 (s, 1H), 7.11 (d, J = 1.2 Hz, 2H). 13 C NMR (126MHz, benzene-d6) δ140.87, 140.75, 137.49 (d, J = 3.8Hz), 135.11 (q, J = 31.7Hz), 133.26 (q, J = 33.0Hz), 132.03 (q, J = 33.6Hz), 128.29, 127.34(q,J=3.8Hz), 127.11(q,J=4.0Hz), 127.01(q,J=4.0Hz), 124.46(q,J=274.3Hz), 123.70(q,J=273.2Hz), 123.49(q,J=272.9Hz). 19 F NMR (376 MHz, benzene-d6) δ -56.98, -63.43, -63.47. 11 BNMR (160 MHz, benzene-d6) δ 64.37.

[0140] Catalyst sample C6, (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane, was prepared as follows:

[0141] Preparation of lithium diisopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0142]

[0143] To a cold (between -101°C and -99°C, CO2(s), then N2(l) methanol bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (3.000 g, 10.24 mmol) in diethyl ether (150 mL) was added n-butyl lithium (4.00 mL, 2.535 M in hexane, 10.14 mmol) with stirring. The reaction mixture was stirred at about -100°C for 2 hours and then allowed to warm to -78°C. Bis(isopropoxy)(3,5-bis(trifluoromethyl)phenyl)borane (3.510 g, 10.26 mmol) in diethyl ether (10 mL) was slowly added. The reaction mixture was allowed to warm to ambient temperature while stirring overnight. Volatiles were removed from the pale yellow, almost clear solution under reduced pressure to give a crystalline solid. The solid was dissolved in diethyl ether (10 mL) and placed in a freezer. No precipitation. The ether was evaporated and the yellow solid was dissolved in hexane, filtered and concentrated under a stream of nitrogen to give a crystalline solid. The supernatant was removed and the solid was dried under reduced pressure. Yield of colorless crystals from the first batch: 3.318 g. NMR analysis of the crystals showed pure desired compound. The supernatant was placed in a freezer overnight. A crystalline material was formed. The supernatant was sucked off and discarded. The crystalline residue was dried under reduced pressure: 2.017 g. Total yield: 5.335 g, 82.79%.

[0144] 1 H NMR (400MHz, benzene-d6) δ8.39(s,2H),8.26(s,1H),7.90(dq,J=1.8,0.9Hz,1H),7.56(d,J=8.2Hz,1H),7.27(ddt,J=7.9,1.7,0.8 Hz, 1H), 3.18 (hept, J = 6.0Hz, 2H), 2.92 (q, J = 7.1Hz, 4H), 0.89 (t, J = 7.1Hz, 6H), 0.78 (d, J = 6.1Hz, 6H), 0.68 (d, J = 6.0Hz, 6H). 13 C NMR (101MHz, benzene-d6) δ153.10, 136.65 (q, J = 29.6Hz), 134.81 (dd, J = 2.7Hz, 1.9 Hz),133.93(q,J=3.6Hz),131.93(q,J=31.6Hz),131.35,129.76(q,J=31.9H z),127.26(q,J=274.6Hz),125.17(d,J=272.4Hz),124.89(q,J=272.8Hz),1 23.25(q,J=3.9Hz), 119.89(p,J=3.9Hz), 66.42, 64.08, 25.49, 24.57, 14.36. 19F NMR (376 MHz, benzene-d6) δ -55.79, -62.66, -63.30. 11 B NMR (160 MHz, benzene-d6) δ 5.32.

[0145] Preparation of Isopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane

[0146]

[0147] To a solution of lithium (diethyl etherate)diisopropoxy-(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate (3.318 g, 5.21 mmol) in diethyl ether (10 mL) was added trimethylchlorosilane (2.0 mL) and a precipitate quickly formed. The reaction mixture was allowed to stir overnight. The reaction mixture was filtered and the volatiles were removed under reduced pressure. NMR analysis showed the reaction was complete. Some putative TMS-O-iPr ether was also present. A second batch of lithium diisopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate (2.017 g, 3.17 mmol, lithium salt; 2.0 mL TMSCl) prepared as described above was treated similarly and stirred for 3 hours. Total amount of combined reagents: 5.335 g, 8.39 mmol; TMSCl: 4.0 mL, 31.6 mmol. The second reaction mixture was filtered and combined with the first reaction product. All volatiles were removed under reduced pressure. The residue was extracted with hexanes, filtered, and the volatiles were removed under reduced pressure at 40°C overnight to give the product as a yellow oil, 3.4703 g, 83.42%.

[0148] 1 H NMR (400MHz, benzene-d6) δ8.05(d,J=1.8Hz,2H),7.80(d,J=2.3Hz,1H),7.34(d,J=1.9Hz,1H),7. 12(d,J=6.5Hz,1H), 7.10(d,J=6.7Hz,1H), 3.78(hept,J=6.1Hz,1H), 0.85(d,J=6.1Hz,6H). 13C NMR (101MHz, benzene-d6) δ139.07, 136.28, 135.37 (q, J = 31.8Hz), 134.93 (d, J = 3.9Hz), 133.49 (q, J = 32.7Hz), 131.50 (q, J = 33.0Hz), 127.87, 126.95 (dq, J=7.5, 3.7Hz), 126.46 (q, J=3.7Hz), 125.41 (hex, J=3.8Hz), 124.57 (q, J=273.9Hz), 123.98 (q, J=272.8Hz), 123.90 (q, J=273.0Hz), 72.49, 23.71. 19 F NMR (376 MHz, benzene-d6) δ -60.31, -63.27 (d, J = 3.3 Hz), -63.47 (d, J = 3.3 Hz). 11 B NMR (160 MHz, benzene-d6) δ 41.28.

[0149] Preparation of Lithium Isopropoxybis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borate

[0150]

[0151] n-Butyl lithium (2.40 mL, 2.535 M in hexane, 6.08 mmol) was slowly added 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). 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 diethyl ether (18 mL) was slowly added. The reaction mixture was stirred at -78 ° C for several hours. The solution was allowed to warm to ambient temperature while stirring overnight to give a pale yellow clear solution. Volatiles were removed from the reaction mixture to give a yellow oil. The oil was extracted with benzene. There was no insoluble matter. Volatiles were removed from the reaction mixture to give a yellow oil. The yield was 4.21 g, 87.6%.

[0152] 1H NMR (400MHz, benzene-d6) δ8.30(s,2H),8.12(s,2H),7.65(dt,J=1.7,0.9Hz,1H),7.27(d,J=8.2Hz,2H),7.08(d,J =8.2Hz, 2H), 3.87 (hept, J = 6.2Hz, 1H), 2.91 (q, J = 7.1Hz, 4H), 0.65 (d, J = 6.2Hz, 6H), 0.63 (t, J = 7.1Hz, 6H). 13 C NMR (101MHz, benzene-d6) δ157.17, 156.73, 134.42, 133.88 (q, J = 3.6Hz), 133.04 (d,J=28.4Hz),132.88(q,J=32.1Hz),129.95(q,J=31.9Hz),127.74(q,J=2 73.6Hz),127.33(q,J=6.9Hz),124.97(q,J=272.4Hz),124.50(q,J=273.0H z), 122.72 (q, J = 3.8Hz), 118.78 (p, J = 4.1Hz), 65.88, 65.34, 25.11, 13.91. 19 F NMR (376 MHz, benzene-d6) δ -56.31, -62.89, -63.76. 11 B NMR (160 MHz, benzene-d6) δ 2.98.

[0153] Preparation of Bis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borane

[0154]

[0155] To a solution of (diethyl ether)isopropoxy-bis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)lithium borate (3.915 g, 4.95 mmol) in diethyl ether (150 mL) was added trimethylchlorosilane (1.10 mL, 10.1 mmol) with stirring. Within 15 minutes, a precipitate formed in the solution. The reaction mixture was stirred overnight. The mixture was filtered and the volatiles were removed under reduced pressure to give a colorless solid, 3.260 g. The product was extracted with hexane, filtered, and the volatiles were removed under reduced pressure to give the product as a light solid, 3.109 g, 96.53%.

[0156] 1 H NMR (500 MHz, benzene-d6) δ 7.90 (s, 1H), 7.83 (s, 1H), 7.66 (s, 3H), 7.09 (s, 5H), 7.09 (s, 5H).13 C NMR (126MHz, benzene-d6) δ141.54, 140.05, 138.35 (q, J = 3.8Hz), 135.84 (q, J = 32.0Hz), 133.02 (q, J = 33.0Hz), 132.02 (q, J = 33.7Hz), 129.98 ( q, J=3.5Hz), 128.29, 127.91 (d, J=2.4Hz), 127.13 (q, J=4.2Hz), 124.15 (q, J=274.2Hz), 123.70 (q, J=273.2Hz), 123.37 (q, J=273.2Hz). 19 F NMR (470 MHz, benzene-d6) δ -56.40, -63.31, -63.58. 11 BNMR (160 MHz, benzene-d6) δ 67.58.

[0157] Catalyst sample C7 was prepared as follows:

[0158] Preparation of tris(2,5-bis(trifluoromethyl)phenyl)borane

[0159]

[0160] The reaction was performed in a manner similar to previously reported procedures. 2 Isopropylmagnesium chloride-lithium chloride (46.0 mL, 58.0 mmol, 1.26 M in THF) was added to a solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (17.05 g, 58.2 mmol) in THF (250 mL) in an acetone bath cooled with dry ice (-76 ° C). After the addition was complete, the reaction flask was transferred to an ice bath (0 ° C) and the reaction mixture was stirred for 2 hours. The reaction mixture was cooled to -78 ° C and 15 mL of boron trifluoride diethyl etherate (2.43 mL, 2.74 g, 19.3 mmol) in ether was added. The reaction mixture was allowed to warm to room temperature while stirring it over the weekend. Volatiles were removed from the solution to give a reddish solid, 12.77 g. The residue was extracted with toluene and filtered. Volatiles were removed under reduced pressure to give a pink powder, 10.75 g. The solid was extracted with dichloromethane to give a light purple solution. The solution was placed in a freezer overnight. The supernatant was decanted from the very light pink crystalline material that formed. The material was dried overnight under reduced pressure. Yield: 7.0003 g, 55.73%.

[0161] Products without TH: 1H NMR (400 MHz, benzene-d6) δ 7.57 (s, 1H), 7.13 (s, 3H), 7.08 (dd, J=8.3, 1.8 Hz, 3H). 13 C NMR (101MHz, benzene-d6) δ141.10, 136.50 (q, J = 32.2Hz), 132.81 (q, J = 33.1Hz), 131.59 (q, J = 3.8Hz), 128.85(q,J=3.7Hz), 127.45(q,J=3.4,2.1Hz), 123.93(q,J=274.6Hz), 123.59(q,J=273.1Hz). 19 F NMR (376 MHz, benzene-d6) δ -56.48, -63.77. 11 B NMR (160 MHz, benzene-d6) δ 68.81.

[0162] Catalyst sample C8, bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct, was prepared as follows:

[0163] Preparation of lithium (tetrahydrofuran)bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)isopropoxyborate

[0164]

[0165] n-Butyl lithium (3.00 mL, 2.54 M in hexane, 7.61 mmol) was added to a cold (between -101 ° C and -99 ° C, CO2 (s), then N2 (l) methanol bath) solution of 1-bromo-2,3,5,6-tetrafluoro-4-trifluorotoluene (2.26 g, 7.61 mmol) in diethyl ether (100 mL) under stirring. The reaction mixture was stirred at -100 ° C for 2 hours and then warmed to -76 ° C. Bis (3,5-bis (trifluoromethyl) phenyl) isopropoxy-borane (3.78 g, 7.61 mmol) in diethyl ether (10 mL) was slowly added to the reaction mixture. The reaction mixture was slowly warmed to ambient temperature while stirring overnight. The next day, the pale yellow almost clear solution was filtered, and the volatiles were removed from the filtrate under reduced pressure to obtain a crystalline solid. The solid was washed with hexane, filtered and dried under reduced pressure. An aliquot of the solid was taken for NMR analysis. It has limited solubility in benzene. An aliquot was dissolved in THF and the volatiles removed under reduced pressure and then analyzed again by NMR in benzene. Yield: 6.16 g, 93.2%.

[0166] 1H NMR (500MHz, benzene-d6) δ8.32 (s, 4H), 7.85 (s, 2H), 3.47 (h, J = 6.2Hz, 1H), 3.26-3.17 (m, 4H), 1.24-1.16 (m, 4H), 0.55 (d, J = 6.2Hz, 6H). 13 C NMR (126MHz, benzene-d6) δ 144.07 (d, J = 259.4Hz), 134.41, 133.82, 133.48 (d, J = 187.5Hz), 130.59 (q, J = 32.2Hz), 130.45 (q, J = 31.8Hz), 126.40-1 23.43 (m), 125.84, 124.97 (q, J = 272.4Hz), 119.94 (p, J = 4.0Hz), 118.92 (d, J = 190.9Hz), 109.57 (d, J = 22.7Hz), 68.38, 65.30, 25.64, 25.13. 19 F NMR (470 MHz, benzene-d6) δ -56.26 (t, J = 20.7 Hz), -62.59, -137.04, -141.73. 11 B NMR (160 MHz, benzene-d6) δ 1.20.

[0167] Preparation of Bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane Tetrahydrofuran THF Adduct

[0168]

[0169] To a solution of lithium (tetrahydrofuranyl)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 trimethylsilyl chloride (2.00 mL, 18.4 mmol) with stirring. The reaction mixture was stirred overnight. The next day, the reaction mixture was heated to 40 ℃ and then stirred for 2 hours. The reaction mixture was stirred for 2 hours. The reaction mixture was stirred for 3 ... 19 F NMR spectroscopy analysis of an aliquot of the reaction mixture revealed no reaction. A solution of hydrogen chloride in diethyl ether (7.00 mL, 2.0 M, 14.0 mmol) was added and the reaction mixture was stirred overnight. The next day, the reaction mixture was stirred overnight by 19F NMR spectroscopy analysis of an aliquot of the reaction mixture revealed that the reaction was complete. The mixture was filtered and the volatiles were removed from the filtrate under reduced pressure. The resulting residue was dissolved in toluene, filtered, and the volatiles were removed from the filtrate under reduced pressure to give 4.50 g of crude product. The colorless pasty solid was washed with hexane and filtered to give a colorless powder which was dried under reduced pressure. NMR analysis of the powder revealed that one molecule of isopropanol was retained in the coordination sphere of borane. Yield of borane as isopropanol adduct: 2.45 g, 52.8%.

[0170] A portion of borane isopropanol adduct (1.811 g) was dissolved in ether (40 mL) and THF (10 mL) was added to the solution. The solution was slowly evaporated to obtain large crystals. The supernatant was removed and the very light 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 borane isopropanol adducts. THF did not replace the coordinated alcohol. The supernatant solution and hexane washings from the crystals were combined and concentrated under vacuum to obtain a second batch of crystals (0.422 g). The second batch of crystals was washed and dried in the same manner as the first batch. NMR analysis showed the presence of coordinated isopropanol, but little or no THF. THF was added and then volatiles were removed under reduced pressure. NMR analysis showed the presence of THF, but there was still some isopropanol. The solid was dissolved in THF and then pumped out. Repeat five more times to obtain a THF adduct as a white powder. Yield: 0.413 g, 22.4%.

[0171] THF adduct:

[0172] 1 H NMR (400MHz, benzene-d6) δ7.87(s,4H),7.80(s,4H),3.02-2.93(m,4H),0.78-0.72(m,4H). 13 C NMR (126MHz, benzene-d6) δ147.98 (td, J=16.5, 3.6Hz), 146.05 (tt, J=11.8, 4.1Hz), 145.58 (d, J=20.9Hz), 143.50 (d, J=20.1Hz), 133.4 4,131.39(q,J=32.6Hz),124.24(q,J=272.7Hz),121.78(t,J=4.0Hz),121.45(q,J=274.4Hz),109.38-108.10(m),73.75,23.90. 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 B NMR (160 MHz, benzene-d6) δ 7.22.

[0173] A catalyst sample prepared as described above in Reference Example 2 is shown below.

[0174]

[0175] The structures of fluorinated aryl borane Lewis acid catalyst samples C1-C8 and commercially available FAB are shown above. Structure C1 is tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct (corresponding to the starting material A1 in the claims). Structure C2 is bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct (corresponding to the starting material A2 in the claims). Structure C3 is bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct (corresponding to the starting material A3 in the claims). Structure C4 is bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct (corresponding to the starting material A4 in the claims). Structure C5 is bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane (corresponding to the starting material A5 in the claims). Structure C6 is (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane (corresponding to the starting material A6 in the claims). Comparative structure C7 is tris(2,5-bis(trifluoromethyl)phenyl)borane. Structure C8 is bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct (corresponding to the starting material A7 in the claims).

[0176] Reference Example 3 - Screening Studies

[0177] The SiH coupling of fluorinated triarylborane Lewis acids prepared as described above in the presence of water was evaluated 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., FAB, 30.7 mg dissolved in 5 mL of toluene). Silane (e.g., TES, 38.4 μL, 2 eq.), internal standard (IS, mesitylene, 16.8 μL, 1 eq.) was placed in an NMR tube. The catalyst (0.5 mL, 5 mol%) was delivered via a pipette as a toluene stock solution. The tube was capped and acquired at fixed time intervals.1 H NMR spectroscopy. After 2 and 24 hours, the conversion was determined in comparison with an internal standard (Si-H bonds to IS or product to IS when possible).

[0178]

[0179] SiH coupling reaction in the presence of water.

[0180] Table 2: SiH coupling reactions in the presence of water

[0181]

[0182] Without being bound by theory, it is believed that C7 is sterically too large to catalyze the SiH coupling reaction under the conditions tested and this demonstrates that not all fluorinated arylboranes can catalyze this reaction.

[0183] Reference Example 4 - Preparation of SiH-containing polyolefin copolymer (ethylene, octene and 5-hexenyl dimethylsilane) General procedure for the preparation of copolymers of 7-octenyldimethylsilane (HDMS) or 7-octenyldimethylsilane (ODMS)

[0184] Batch reactor polymerization was carried out in a 2L Parr batch reactor. The reactor was heated by an electric heating jacket and cooled by an internal serpentine cooling coil containing cooling water. The reactor and the heating / cooling system were controlled and monitored by a CAMILE TG process computer. The bottom of the reactor was equipped with a dump valve that emptied the reactor contents into a stainless steel dump pot. The dump pot was discharged to a 30-gallon blowdown tank, where both the pot and the tank were purged with nitrogen. Before use, all solvents used for polymerization or catalyst replenishment were run through a solvent purification column to remove any impurities that might affect polymerization. 1-Octene and ISOPARE were passed through two columns, the first containing A2 alumina and the second containing Q5 reactants. (ISOPAR-E is an isoparaffin fluid that typically contains less than 1 ppm of benzene and less than 1 ppm of sulfur, which is commercially available from ExxonMobil Chemical Company). Ethylene was passed through 2 columns, the first containing A204 alumina and mol molecular sieve, and the second contains Q5 reactant. The N2 used for transfer is passed through a stream containing A204 alumina, Single column of molecular sieves and Q5 reactants.

[0185] The desired amount of 5-hexenyldimethylsilane monomer or 7-octenyldimethylsilane monomer is added to the loading column via a spray tank, followed by the addition of ISOPAR-E solvent and / or 1-octene, depending on the desired reactor loading. The loading column is filled to the loading set point by using a laboratory scale to which the loading column is mounted. After the addition of the liquid feed, the reactor is heated to the polymerization temperature set point. If ethylene is used, it is added to the reactor while the reactor is at reaction temperature to maintain the reaction pressure set point. The amount of ethylene added is monitored by a micromotion flow meter.

[0186] In an inert atmosphere glove box, scavenger MMAO-3A is processed, extracted into a syringe and transferred to a catalyst injection tank under pressure. Then rinse with toluene 3 times, 5mL each time, and then injected into the reactor. The primary catalyst and activator are mixed with an appropriate amount of purified toluene to obtain the required molar concentration solution. The catalyst and activator are processed in an inert atmosphere glove box, extracted into a syringe, and transferred to a catalyst injection tank under pressure. Subsequently rinse with toluene 3 times, 5mL each time. Start the running timer immediately after adding the catalyst. If ethylene is used, it is added by CAMILE to maintain the reaction pressure set point in the reactor. These polymerizations run for 10 minutes, then stop the agitator, and open the bottom dump valve to empty the reactor contents into the dump pot. The dump pot contents are poured into a tray placed in an experimental fume hood, and the solvent is evaporated overnight in this laboratory fume hood. The tray containing the remaining polymer is then transferred to a vacuum oven, in which it is heated to up to 140°C under vacuum to remove any remaining solvent. After the trays cooled to ambient temperature, the polymer was weighed to obtain yield / efficiency and submitted for polymer testing.

[0187] Copolymer samples were prepared using the following conditions according to the batch reactor process: for the first copolymer in Table 3, 120°C, 12 g of loaded ethylene, 3.5 mL of 5-hexenyldimethylsilane, 52 g of 1-octene, 588 g of ISOPAR E, 20 μmol of MMAO-3A, ​​1.2 equivalents of bis(hydrogenated tallow alkyl)methylammonium tetra(pentafluorophenyl)borate to 1.0 equivalent of the main catalyst; for the second copolymer in Table 3, 120°C, 12g of loaded ethylene, 4mL of 7-octenyldimethylsilane, 58g of 1-octene, 596g of ISOPAR-E, 20 μmol of MMAO-3A, ​​1.2 equivalents of bis(hydrogenated tallow alkyl)methylammonium tetra(pentafluorophenyl)borate to 1.0 equivalent of the main catalyst; for the third copolymer in Table 3, 120°C, 12g of loaded ethylene, 4mL of 7-octenyldimethylsilane, 58g of 1-octene, 592g of ISOPAR-E, 20 μmol of MMAO-3A, ​​1.2 equivalents of bis(hydrogenated tallow alkyl)methylammonium tetra(pentafluorophenyl)borate to 1.0 equivalent of the main catalyst. The amount of the primary catalyst was adjusted to achieve the desired efficiency. The reactor pressure and temperature were kept constant by feeding ethylene during the polymerization reaction and cooling the reactor as needed. The polymerization was carried out to an ethylene uptake of 23 g. All polymerizations were performed with bis(hydrogenated tallow alkyl)methylammonium tetra(pentafluorophenyl)borate as the activator and MMAO as the scavenger. The properties of the silicone-polyolefin copolymer (elastomer) are shown in Table 3.

[0188] Table 3: Silicone-polyolefin copolymer (elastomer) information

[0189]

[0190] Reference Example 5 - Crosslinking Studies with SiH-Functional Polyolefin Copolymers

[0191] Samples of fluorinated triarylborane Lewis acids C4, C5, C6 and C7 prepared as described above were selected to determine their feasibility of catalyzing the reaction of silicon-bonded hydrogen atoms in copolymers of ethylene, 1-octene and HDMS or ODMS prepared as described in Reference Example 4. Commercially available tris(pentafluorophenyl)borane (FAB) was used as a control.

[0192] Solutions of these fluorinated triaryl borane Lewis acids (boranes) are prepared by first weighing solid borane in a glove box under a nitrogen atmosphere. Borane is then taken out of the glove box and mixed with toluene of known mass to prepare a solution that can be blended into the molten copolymer. The time of exposure to air is carefully limited before the solution is produced, and toluene dried on the molecular sieve is used as a solvent. All tests of the catalyst-loaded elastomer samples start within 48 hours of taking out the catalyst sample from a nitrogen atmosphere for limiting air or moisture contamination. Solutions of C4, C5, C6 and C7 are added to the melt blending process so that the loading of each borane is 100ppm. Melt blending is performed using a Haake blender with a 20g bowl, wherein the temperature is set to 80°C and the blending rate used is 60rpm. 10g of the elastomer described in Table 3 is blended for 3 minutes until fully melted, and then 100 μL of borane solution is added. The system is blended for another 3 minutes until fully homogenized, and then the resulting catalyst-loaded elastomer is taken out and cooled. There was no visual evidence of premature crosslinking of the elastomer during melt blending with the C4, C5, C6 and C7 solutions. Premature crosslinking was visually observed when the FAB solution was used in the same process.

[0193] The resulting catalyst-loaded elastomer was then compression molded into torsion bars (2 mm thick) by compression molding at 90° C. for 4 minutes at a force of 20,000 lbs. These torsion bars were then moisture cured by exposure to a humid environment controlled at 85° C., 85% relative humidity or 25° C., 85% relative humidity. The bars were removed from the humid environment after 1 or 5 days to give some idea of ​​the kinetics of the moisture curing reaction. After the bars were removed from the humid environment for testing, they were discarded and not used for further testing.

[0194] Reference Example 6 - Analysis of samples

[0195] The torsion bars were tested by dynamic mechanical analysis (DMA) using an ARES rheometer. The samples were fixed in the instrument and exposed to a temperature sweep from 25°C to 250°C, a temperature ramp of 2°C / min, and a 1% strain. The crosslinking of the moisture cure was monitored by evidence of a temperature-insensitive storage modulus plateau.

[0196] The DMA shear storage modulus of the samples containing C4 borane exposed to moisture at 85°C for 1 day decreases monotonically with temperature and decreases to about 10 2 Pa, indicating that minimal crosslinking has occurred during the exposure. After 5 days of exposure to moisture, the DMA shear storage modulus of the sample decreases with temperature until the sample reaches approximately 160°C. The sample then shows a decrease of approximately 10 4The shear storage modulus plateaus at 1.37°C, indicating that a cross-linked network has formed, preventing the sample from further melting as the temperature increases. This test demonstrates the efficacy of C4 borane as a latent condensation catalyst in polymer systems.

[0197] The DMA shear storage modulus of the samples containing C5 borane exposed to moisture at 85 °C for 1 day decreases monotonically with temperature and decreases to about 10 4 Pa, indicating that minimal cross-linking has occurred during the exposure. After 5 days of exposure to moisture, the DMA shear storage modulus of the sample decreases with temperature until the sample reaches 170°C.

[0198] Then the sample showed about 10 4 The shear storage modulus plateaus at 1.37°C, indicating that some crosslinking has occurred, thereby preventing the sample from further melting as the temperature increases. This test demonstrates the efficacy of C5 borane as a latent condensation catalyst in a polymer system.

[0199] The DMA shear storage modulus of the samples containing C6 borane exposed to moisture at 85 °C for 1 day decreases monotonically with temperature and decreases to about 10 3 Pa, indicating that minimal crosslinking has occurred during the exposure. After 5 days of exposure to moisture, the DMA shear storage modulus of the sample decreases with temperature until the sample reaches approximately 160°C. The sample then shows a decrease of approximately 10 4 The shear storage modulus plateaus at 1.37°C, indicating that a cross-linked network has formed, preventing the sample from further melting as the temperature increases. This test demonstrates the efficacy of C6 borane as a latent condensation catalyst in polymer systems.

[0200] The DMA shear storage modulus of the samples containing C5 borane exposed to moisture at 25° C. for 1 day and 5 days decreased monotonically with temperature and to the same extent as the samples without any moisture treatment, indicating that minimal crosslinking had occurred during the moisture exposure at 25° C. This test, compared to the test of the samples containing C5 exposed to moisture at 85° C., demonstrates that heating is necessary for C5, a latent condensation catalyst, to effectively cure the polymer system.

[0201] The DMA shear storage modulus of the samples containing C7 exposed to moisture for 1 day and 5 days at both 25° C. and 85° C. decreased monotonically with temperature and to the same extent as the samples without any moisture treatment, indicating that minimal crosslinking has occurred during moisture exposure at 25° C. and 85° C. Both tests demonstrate that C7 does not adequately act as a catalyst at temperatures both below and above the melting point of the polymer system under the conditions tested.

[0202] The torsion bars were analyzed using ATR FT-IR spectroscopy at time points of interest to monitor the formation of Si-O-Si bonds and the loss of Si-H bonds. The characteristic vibrational frequencies monitored for this study are summarized in Table 4.

[0203] Table 4: Characteristic vibration frequencies of Si-H and Si-O-Si groups

[0204] Functional Group <![CDATA[Frequency (cm -1 )]]> Si-H 890,2080-2280 Si-O-Si 1000-1130

[0205] The spectra of the analyzed boranes (C4 and C5) show the siloxane peak region (1000 cm -1 -1130cm -1 ) gradually increases with time. The two peaks related to Si-H vibration (890cm -1 and 2080cm -1 Up to 2280cm -1 ) also decreases at longer times, indicating a loss of Si-H bonds. The combination of these observations leads to the conclusion that at least some of these Si-H groups react to give siloxane bonds (Si-O-Si bonds). Additional side reactions may have occurred, as evidenced by the presence of a small increase in the Si-H group at about 1710 cm-1 in both cases. -1 . It was also observed that there was still a large amount of unreacted Si-H content in the system, which could continue to react for a longer time or be too immobilized in the partially crosslinked matrix to have the mobility to complete the crosslinking reaction with other unreacted Si-H groups. Additional loadings of these boranes were not tested, however it is assumed that higher loadings would result in more complete utilization of the Si-H content of the copolymer and a greater corresponding crosslink density.

[0206] These boranes present a practical, controllable route to achieve moisture cure of Si-H containing copolymers. FTIR spectroscopy revealed that the SiH peak in the C7 sample showed little change over time, consistent with studies of model systems in which C7 did not catalyze any SiH conversion under the conditions tested.

[0207] Industrial Applicability

[0208] As demonstrated in the examples shown above, when starting material B) comprises a silyl hydride functional polyolefin, starting material A) and starting material B) can be combined, e.g., mixed, and unless and until starting material A) and starting material B) are exposed to water, starting material A) and starting material B) do not cure, and until starting material A) and starting material B) are exposed to water, starting material A) and starting material B) cure. The fact that the silyl hydride (SiH functional material) and catalyst can be combined and stored prior to use / curing is an unexpected benefit of the compositions and methods described herein.

[0209] Issues to be resolved

[0210] The catalysts predominantly employed in the preparation of siloxane intermediates and siloxane cured networks from Si-H functional silanes and siloxanes are platinum-based catalysts, which have certain disadvantages as described above. An emerging alternative to Pt-based catalysts is the use of tris(pentafluorophenyl)borane (B(C6F5)3), referred to herein as FAB. FAB is relatively low cost, does not contain heavy metals, and has a low level of catalysis required. The use of FAB as a catalyst in a reaction between a Si-H functional group and another functional group that can be used in a curable siloxane composition or as an intermediate has been reported. These functional groups include alkoxysilyl functional groups (≡Si-OR) and silanols (≡Si-OH).

[0211] In the case of FAB-catalyzed coupling reactions between ≡Si-H and ≡Si-OR or between ≡Si-H and ≡Si-OH, a major limitation to commercial applications is that the reaction is highly exothermic and occurs very rapidly at room temperature. In the case of large-scale production of siloxanes, this is problematic because of 1) the rapid generation of flammable gases and 2) the rapid heating of the reaction mixture. The combination of these factors makes commercial-scale practice difficult to control and makes proper reaction feeding / mixing and monitoring difficult, which can lead to poor reproducibility.

[0212] There is a need in the industry for alternative catalysts that can promote the reaction between two Si-H moieties in the presence of water in a more controlled manner than FAB. It would be particularly desirable to have the ability to control this rate based on the choice of catalyst.

[0213] Solution

[0214] 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.

[0215] Definition and usage of terms

[0216] Abbreviations used in the specification have the definitions in Table 5 below.

[0217] Table 5 - Abbreviations

[0218]

[0219]

[0220] Unless otherwise specified, all amounts, ratios and percentages are by weight. The amount of all starting materials in the composition totals 100 weight %. Summary of the invention and description abstract are hereby incorporated by reference. Unless otherwise specified in the context of this specification, the articles "one", "a kind of" and "said" each refer to one (a kind) or more (multiple). Unless otherwise specified, the singular includes plural meanings. The disclosure of a range includes the range itself and any value and endpoints contained therein. For example, the disclosure of a range of 2.0 to 4.0 not only includes a range of 2.0 to 4.0, but also includes 2.1, 2.3, 3.4, 3.5 and 4.0 and any other number contained in the range individually. In addition, for example, the disclosure of a range of 2.0 to 4.0 includes a subset such as 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7 and 3.8 to 4.0 and any other subset contained in the range. Similarly, disclosure of a Markush group includes the entire group and also includes any individual members and subgroups contained therein. For example, disclosure of the Markush group hydrogen atom, alkyl group, alkenyl group, or aryl group includes the individual member alkyl; the alkyl and aryl subgroups; and any other individual members and subgroups contained therein.

[0221] The term "comprising" and its derivatives, such as "having" and "containing", are used in the broadest sense herein, meaning and encompassing the concepts of "including", "consisting essentially of", and "consisting of". The use of "for example", "for example", "such as", and "including" to list illustrative examples is not meant to be limited to the listed examples. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to" and encompasses other similar or equivalent examples.

[0222] In general, as used herein, a hyphen "-" or dash "-" within a range of values ​​means "to" or "up to"; ">" means "higher than" or "greater than"; "≥" means "at least" or "greater than or equal to"; "<" means "lower than" or "less than"; and "≤" means "at most" or "less than or equal to". Each of the foregoing patent applications, patents, and / or patent application publications is each expressly incorporated by reference in its entirety in one or more non-limiting embodiments.

[0223] It is to be understood that the appended claims are not limited to individual and particular compounds, compositions, or methods described in the detailed description, which may vary between particular embodiments falling within the scope of the appended claims.

Claims

1. A composition comprising: A) 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; 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 A8) A combination of two or more of A1) to A7); and B) Silyl hydrides having at least one silicon-bonded hydrogen atom per molecule.

2. The composition according to claim 1, wherein A) the fluorinated triarylborane Lewis acid is selected from the group consisting of: 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.

3. The composition according to claim 1 or claim 2, wherein B) the silyl hydride is selected from the group consisting of: B1) Formula H k S i 5 (4-k) Silane, where each R 5 independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, and subscript k is 1 to 3; B2) a polyorganohydrogensiloxane comprising two or more siloxane units selected from the group consisting of: 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 , where each R 4 are independently selected monovalent hydrocarbon groups free of aliphatic unsaturation; and B3) a polyolefin having the formula (B3-1): of silicon-bonded hydrogen functional groups, where each R 1 are independently selected monovalent hydrocarbon groups and each subscript a is independently 1 or 2.

4. The composition according to claim 3, wherein B1) is the formula HSiR 5 3 silane, wherein each R 5 is an alkyl group of 1 to 6 carbon atoms; B2) is a polydiorganohydrogensiloxane having the following 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 as described above, and the values ​​of the subscripts g, h, i, and j are such that g ≥ 0, h ≥ 0, the average value of the quantity (g+h) is 2, i ≥ 0, j ≥ 0, and the quantity (g+j) ≥ 1, and the quantity (i+j) is in the range of 0 to 1000; and B3) is a SiH functional polyolefin selected from the group consisting of: Unit formula (B3-2): Where R 1 and subscript a as above, each D 1 is independently a divalent hydrocarbon group of 2 to 50 carbon atoms, each R 25 are independently H, a monovalent hydrocarbon group of 1 to 18 carbon atoms, or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms, and the values ​​of the subscripts M and N are such that 1≤M≤10 and 10 <N<20,000; Unit type (B3-3): where the subscripts a and R 1 As described above, the subscript f is 0 or 1, the subscripts t and u are decimals, and the relative values of the decimals are such that 0 < t ≤ 1, 0 ≤ u ≤ 1, the subscript g is 1 or greater, and each R et represents an ethylene unit, and each R O represents an olefin unit other than ethylene; and unit type (B3-4): The subscripts a, f, g, t, and u, as well as R 1 As mentioned above, each R 7 are independently monovalent hydrocarbon groups having 1 to 20 carbon atoms.

5. A method for forming a product having siloxane bonds, the method comprising: 1) Combining starting materials, the starting materials 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; 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; as well as A8) a combination of two or more of A1) to A7); B) a silyl hydride having at least one silicon-bonded hydrogen atom per molecule, and C) Water; The silicon-bonded hydrogen atoms are thereby reacted to form the siloxane bonds and byproducts comprising hydrogen gas.

6. The process according to claim 5, wherein the starting material A) is selected from the group consisting of: 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.

7. The method according to claim 5, wherein B) the silyl hydride is selected from the group consisting of: B1) Formula H k S i 5 (4-k) Silane, where each R 5 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; B2) a polyorganohydrogensiloxane comprising two or more siloxane units selected from the group consisting of: 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 , where each R 4 are independently selected monovalent hydrocarbon groups free of aliphatic unsaturation; and B3) a polyolefin having the formula (B3-1): of silicon-bonded hydrogen functional groups, where each R 1 are independently selected monovalent hydrocarbon groups and each subscript a is independently 1 or 2.

8. The method according to claim 7, wherein: The starting material B1) is of the formula HSiR 5 3 silane, wherein each R 5 is an alkyl group of 1 to 6 carbon atoms; The starting material B2) is a polydiorganohydrogensiloxane having the following 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 as described above, and the values ​​of the subscripts g, h, i, and j are such that g ≥ 0, h ≥ 0, the average value of the quantity (g+h) is 2, i ≥ 0, j ≥ 0, and the quantity (g+j) ≥ 1, and the quantity (i+j) is in the range of 0 to 1000; and The starting material B3) is a SiHH-functional polyolefin copolymer selected from the group consisting of: Unit type (B3-2): Where R 1 and subscript a as above, each D 1 is independently a divalent hydrocarbon group of 2 to 50 carbon atoms, each R 25 are independently H, a monovalent hydrocarbon group of 1 to 18 carbon atoms, or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms, 1≤M≤10, and 10 <N<20,000; Unit type (B3-3): where the subscripts a and R 1 As described above, the subscript f ranges from 0 to 1, the relative values of the subscripts t and u are such that 0 < t ≤ 1, 0 ≤ u ≤ 1, the subscript g is 1 or greater, and each R et represents an ethylene unit, and each R O represents an olefin unit other than ethylene; as well as Unit type (B3-4): The subscripts a, f, g, t, and u, as well as R 1 As mentioned above, each R 7 are independently monovalent hydrocarbon groups having 1 to 20 carbon atoms.

9. The method according to any one of claims 5 to 8, wherein the combining in step 1) comprises mixing starting material A), starting material B) and starting material C) in any order and heating.

10. The process according to any one of claims 5 to 8, wherein the starting material A) is dissolved in a solvent before step 1).

11. The process according to any one of claims 5 to 8, wherein starting material A) and starting material B) are combined before step 1).

12. The method according to any one of claims 5 to 8, further comprising: The residual fluorinated triarylborane Lewis acid in the product is neutralized.

13. The method according to any one of claims 5 to 8, further comprising: During and / or after step 1), the by-product comprising H2 is removed.

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