Method for producing polyfunctional organosiloxane and composition containing same

Abstract

The polyfunctional organohydrogensiloxane is prepared using a fluorinated triarylborane Lewis acid as a catalyst. The polyfunctional organohydrogensiloxane can be incorporated into a release coating composition. Alternatively, the polyfunctional organohydrogensiloxane can be further functionalized with a curable group to form a clustered functional organosiloxane. The clustered functional organosiloxane can be incorporated into a thermal radical curing adhesive composition.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 63 / 043,152, filed June 24, 2020. U.S. Provisional Patent Application No. 63 / 043,152 is incorporated herein by reference.

[0002] A method for producing polyfunctional organosiloxanes is disclosed. The polyfunctional organosiloxanes comprise a linear polydiorganosiloxane backbone with cyclic siloxane endblockers. The polyfunctional organosiloxanes are useful in curable compositions, for example, as crosslinkers. [Background technology]

[0003] Methods for producing polyfunctional organosiloxane crosslinkers having a linear polydiorganosiloxane backbone with a cyclic siloxane endblocker have been proposed, using a platinum catalyst to react a cyclic polyorganohydrogensiloxane with a vinyl-terminated or hydroxyl-terminated polydiorganosiloxane. These methods suffer from the drawback of requiring expensive purification of the cyclic polyorganohydrogensiloxane. These methods also suffer from the drawback of poor control over the structure and molecular weight of the product. Summary of the Invention

[0004] A method for preparing polyfunctional organohydrogensiloxanes using a fluorinated triarylborane Lewis acid as a catalyst is disclosed. The method may further include a step of functionalizing the polyfunctional organohydrogensiloxane to form a clustered functional organosiloxane. The polyfunctional organohydrogensiloxanes and the clustered functional organosiloxanes are useful in curable compositions. DETAILED DESCRIPTION OF THE INVENTION

[0005] The polyfunctional organohydrogensiloxanes prepared by the methods described herein comprise a linear polydiorganosiloxane backbone with cyclic SiH-functional endblockers. The polyfunctional organohydrogensiloxanes can be used as crosslinkers. The polyfunctional organohydrogensiloxanes are useful in curable compositions, such as release coating compositions.

[0006] The method for preparing a product comprising a polyfunctional organohydrogensiloxane comprises: 1) A) fluorinated triarylborane Lewis acids, B) Formula

[0007] [ka] wherein the subscript n is 1 to 2,000, and each R 1 are independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups; and C) Formula, (RHSiO 2 / 2 ) v wherein the subscript v is 3 to 12, and each R is an independently selected monovalent hydrocarbon radical, thereby preparing a product comprising a polyfunctional organohydrogensiloxane and a by-product comprising H. In step 1), the starting materials may optionally further comprise D) a solvent.

[0008] The method may optionally include one or more additional steps. The method may further include a step of recovering the polyfunctional organohydrogensiloxane. The method may further include a step of 2) removing H2 generated during the formation of the polyfunctional organohydrogensiloxane during and / or after step 1), and / or a step of 3) neutralizing any residual fluorinated triarylborane Lewis acid in the product. By-product H2 can be removed by any convenient means, such as stripping and / or combustion. Removal and / or neutralization may be carried out by adding E) a neutralizing agent to the product, followed by filtering the product. Steps 2) and 3) can be carried out in any order. For example, if particulate by-products are present as a result of neutralization, the method may further include a step 4) removing particulates, such as alumina, after neutralization by any convenient means, such as filtration.

[0009] One or more of the process steps can be carried out at a temperature of 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., alternatively 30° C. Alternatively, step 1) can be carried out at a temperature of 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., alternatively 30° C. Without being bound by theory, it is believed that carrying out the process, particularly step 1), at a relatively low temperature (e.g., 90° C. or less, alternatively 80° C. or less, alternatively 70° C. or less, alternatively 50° C. or less) can result in improved reaction rate, yield, or both.

[0010] The starting materials used in step 1) of the process, or steps 1), 2), and 3) of the process, may be free of platinum group metal catalysts. As used herein, "free" includes none, or an amount undetectable by GC, or an amount insufficient to cause performance problems in release coatings prepared from release coating compositions containing polyfunctional organohydrogensiloxanes made by the processes described herein.

[0011] Starting Materials A) Catalyst The starting material A) in the process described herein is a fluorinated triarylborane Lewis acid. The fluorinated triarylborane Lewis acid has the following formula:

[0012] [ka] [In the formula, each R o ortho-substituents, and each R m is a meta-substituent, and each R p is a para substituent and R 2 is optional and comprises a functional group or functional polymer group, and the subscript x is 0 or 1. In the above formula, each R o1-6 , each R m1-6 , and each R p1-3 are independently selected from H, F, or CF3, with the proviso that R o1-6 , R m1-6 , and R p1-3 Not all of the above can be F at the same time, and R o1-6 , R m1-6 , and R p1-3 Not all of the can be H at the same time, and R o1-4 If two or more of are CF3, then R o5 and R o6 are each independently selected from H or F. 2 is optional, i.e., R 2 exists for subscript x=1, and R 2 does not exist when the subscript x=0. R 2 may be a Lewis base that forms a complex with a fluorinated triarylborane Lewis acid, and / or a molecule or moiety that contains at least one electron pair available for forming a coordinate bond with a Lewis acid, and R is described in paragraphs

[0024] to

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

[0013] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , and R o6 may each be H. Alternatively, R o1 , R o2 , R o3 , and R o4 may each be H. Alternatively, R o5 and R o6 may each be F.

[0014] Alternatively, R m1 , R m2 , R m3 , R m4 , R m5 , and R m6 Each of R may be CF3. Alternatively, R m1 , R m2 , R m3 , and R m4 Each of R may be CF3. Alternatively, R m5 and R m6 may each be F. Alternatively, R m5 and R m6 may each be H.

[0015] Alternatively, R p1 , R p2 , and R p3 may each be H. Alternatively, R p1 and R p2 may be H. Alternatively, R p3 may be F. Alternatively, R p3 may be CF3.

[0016] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R o6 , R p1 , Rp2 , and R p3 may each be H. and R m1 , R m2 , R m3 , R m4 , R m5 , and R m6 may each be CF3. The subscript x may be 1. Alternatively, the starting material A) may comprise tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct.

[0017] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R o6 , R m5 , R m6 , R p1 , and R p2 Each of R may be H. m1 , R m2 , R m3 , R m4 , and R p3 may each 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.

[0018] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 , and R p2 Each of R may be H. o5 , R o6 , and R p3 Each may be F. R m1 , R m2 , R m3 , R m4may each 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.

[0019] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 , R p2 , and R p3 Each of R may be H. o5 and R o6 may be F. and R m1 , R m2 , R m3 , and R m4 may each 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.

[0020] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R m6 , R p1 , R p2 , and R p3 may each be H. and R m1 , R m2 , R m3 , R m4 , R m5 , and R o6 may each be CF3. The subscript x may be 0. Alternatively, the starting material A) may include bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane.

[0021] Alternatively, R m1 , R p1 , R o2 , Ro3 , R o4 , R p2 , R p3 , R o5 , and R m6 may each be H. and R o1 , R m2 , R m3 , R m4 , R o6 , and R m5 may each be CF. The subscript x may be 0. Alternatively, the starting material A) may include (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane.

[0022] Or R o1 , R o2 , R o3 , R o4 , R p1 , and R p2 Each of R may be H. o5 , R o6 , R m5 , and R m6 may each be F. and R m1 , R m2 , R m3 , R m4 , and R p3 may each 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.

[0023] Alternatively, the fluorinated triarylborane Lewis acid may be selected from the group consisting of tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct, bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct, and bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane. Alternatively, starting material A) may be bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane.

[0024] Fluorinated triarylborane Lewis acids are known in the art and can be prepared by known methods, for example, the methods disclosed in WO2019 / 055740, particularly in paragraphs

[0052] to

[0096] , by appropriately changing the starting materials.

[0025] The amount of starting material A) will vary depending on the types and amounts of other starting materials used, but starting material A) may be present in an amount of 5 ppm to 6000 ppm, based on the combined weight of starting materials A), B), and C. Alternatively, the amount may be 5 ppm to 600 ppm, or 5 ppm to 500 ppm, or 5 ppm to 100 ppm, on the same basis.

[0026] Starting Material B) Hydroxyl-Functional Organosilicon Compounds The starting material B) is represented by the formula B-1):

[0027] [ka] wherein the subscript n is 1 to 2,000, and each R 1 are independently selected from the group consisting of monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals. Alternatively, the subscript n may have a value such that 2≦n≦2,000, alternatively 2≦n≦1,000, alternatively 5≦n≦900, alternatively 5≦n≦50, alternatively 5≦n≦15. Alternatively, each R 1may be independently selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or halogenated alkyl groups having 1 to 20 carbon atoms. Suitable alkyl groups include methyl, ethyl, and propyl (including n-propyl and isopropyl). Suitable alkenyl groups include vinyl, allyl, and hexenyl. Suitable aryl groups include phenyl, tolyl, and benzyl. Suitable halogenated alkyl groups include chloromethyl, chloropropyl, and trifluoropropyl. Alternatively, each R 1 may be independently selected from the group consisting of methyl, vinyl, phenyl, and trifluoropropyl.

[0028] When the subscript n=1, the starting material B) may be a hydroxyl-functional silane, such as dimethyldisilanol. Hydroxyl-functional silanes are commercially available. Alternatively, when the subscript n≧2, the starting material B) may be a hydroxyl-terminated polydiorganosiloxane. Hydroxyl-terminated polydiorganosiloxanes suitable for use as starting material B) can be prepared by methods known in the art, such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes. An exemplary hydroxyl-terminated polydiorganosiloxane is hydroxyl-terminated polydimethylsiloxane. Suitable hydroxyl-terminated polydimethylsiloxanes are also commercially available from Gelest, Inc. (Morrisville, Pennsylvania, USA), such as, for example, DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S41, DMS-S32, DMS-S33, DMS-S35, DMS-S42, and DMS-S45. The starting material B) can be one hydroxyl-functional organosilicon compound or a combination of two or more different hydroxyl-functional organosilicon compounds.

[0029] Starting Material C) Cyclic Polyorganohydrogensiloxane The starting material C) of the process described herein is a compound of formula C-1), (RHSiO 2 / 2 ) v wherein subscript v is 3 to 12, and each R is an independently selected monovalent hydrocarbon group. Alternatively, subscript v may be 4 to 10, or 4 to 8. Alternatively, subscript v may have an average value of 4 to 6, or 4 to 5, or 4. In formula C-1), R may be an alkyl group having 1 to 6 carbon atoms. Alternatively, R may be methyl, ethyl, or propyl. Alternatively, R may be methyl.

[0030] Examples of suitable cyclic polyorganohydrogensiloxanes for starting material C) include tetramethylcyclotetrasiloxane, pentamethylcyclopentasiloxane, hexamethylcyclohexasiloxane, and combinations of two or more thereof. Suitable cyclic polyorganohydrogensiloxanes are known in the art and are commercially available, for example, from Dow Silicones Corporation (Midland, Michigan, USA).

[0031] The amounts of starting materials B) and C) will vary depending on various factors, including the OH content of B) the hydroxyl-functional organosilicon compound and the silicon-bonded hydrogen (SiH) content of C) the cyclic polyorganohydrogensiloxane, but are sufficient to provide a molar ratio of SiH in starting material C) to OH in starting material B) (SiH:OH ratio) of 4:1 to 40:1, alternatively 5:1 to 20:1, alternatively 5:1 to 10:1.

[0032] Starting material D) Solvent A solvent can be used in the present method. The solvent can facilitate the introduction of certain starting materials, such as starting material A) fluorinated triarylborane Lewis acid. As used herein, a solvent is one that aids in the fluidization of the starting materials but does not essentially react with any of these starting materials. The solvent may be selected based on the solubility of the starting materials and the volatility of the solvent. "Solubility" refers to the solvent being sufficient to dissolve and / or disperse the starting materials. "Volatility" refers to the vapor pressure of the solvent.

[0033] A suitable solvent may be a hydrocarbon. 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.

[0034] The amount of solvent may vary depending on various factors, such as the type of solvent selected and the amounts and types of other starting materials selected, but the amount of solvent may range from 0.1% to 99% by weight, or alternatively from 2% to 50% by weight, based on the total weight of starting materials A), B), and C).

[0035] Starting Material E) Neutralizing Agent Starting material E) is a neutralizing agent that can optionally be used to neutralize starting material A) after the product has been formed. Alumina, triphenylamine, triethylamine, triphenylphosphine, and phenylacetylene are suitable neutralizing agents. Neutralizing agents are known in the art and are commercially available, for example, from Millipore Sigma (St. Louis, Missouri, USA). The amount of neutralizing agent depends on various factors, including the amount of starting material A), but starting material E) may be present in an amount sufficient to provide a weight ratio of neutralizing agent to fluorinated triarylborane Lewis acid (E:A ratio) of 1:100 to 1:1000, alternatively 1:1 to 1000:1, alternatively 1:100 to 1:1. Alternatively, when the neutralizing agent is triphenylphosphine or phenylacetylene, the E:A ratio may be 1:1 to 20:1. Alternatively, when the neutralizing agent is alumina, the E:A ratio may be from 100:1 to 1000:1.

[0036] Product of the method The product of the above process includes a) a polyfunctional organohydrogensiloxane and a by-product containing H. The product has the general formula a-1):

[0037] [ka] wherein the subscripts v and n and the groups R and R 1 is as defined above, provided that one or more of the hydrogen atoms of formula a-1) is a group represented by formula a-2),

[0038] [ka] [wherein each subscript n, subscript p, R, and R 1 are independently selected and may be replaced with groups as described above. Alternatively, the product may comprise a polyfunctional organohydrogensiloxane of the unit formula a-3), [(HRSiO 2 / 2 ) v-1 (-RSiO 2 / 2 )]2[O-(R 1 2SiO2 / 2 ) n ] n’ [(HRSiO 2 / 2 ) v-2 (-RSiO 2 / 2 )2] o’ wherein the subscripts v and n and the groups R and R 1 is as described above, subscript o' is 0 to 100, and subscript n' = (o' + 1). Those skilled in the art will recognize that depending on various factors, such as the relative amounts of starting materials B) and C), the product may contain two or more polyfunctional organohydrogensiloxane species. The polyfunctional organohydrogensiloxane may have an average of more than two cyclic moieties and more than two linear moieties per molecule (when o' > 0). Alternatively, subscript v may have an average value of 5, subscript n may have an average value of 10, subscript n' may be 1 to 2, and subscript o' may be 0 to 1. Alternatively, subscript v may be 5, subscript n may be 10, subscript n' may be 2, and subscript o' may be 1. Alternatively, if the subscript o'=0, then the product is of the formula a-4):

[0039] [ka] wherein the subscripts n and v and the groups R and R 1 is as described above].

[0040] Those skilled in the art will recognize that polyfunctional organohydrogensiloxanes having two or more linear main chains and three or more cyclic groups per molecule may also be formed and present in the product, depending on various factors, such as the ratio of starting material B) to starting material C) selected for the process. The process described herein can, if desired, minimize crosslinking by controlling the structure of the polyfunctional organohydrogensiloxane. For example, by controlling the ratio of cyclic polyorganohydrogensiloxane to hydroxyl-functional organosilicon compound, it is possible to maximize the amount of polyfunctional organohydrogensiloxane of formula a-1), where subscript o'=0, i.e., two cyclic moieties connected via oxygen atoms at the end of the linear polydiorganosiloxane. For example, decreasing the ratio of C) cyclic polyorganohydrogensiloxane to B) hydroxyl-functional organosilicon compound increases the likelihood of forming crosslinked species. Thus, starting materials B) and C) can be used in amounts such that the molar ratio of C):B) is greater than 6:1. Alternatively, starting materials B) and C) can be used in amounts such that the SiH:OH ratio is from 4:1 to 40:1, alternatively from 5:1 to 20:1, alternatively from 5:1 to 10:1. The described methods can optionally further comprise recovering the polyfunctional organohydrogensiloxane from the product by any convenient means, such as stripping and / or distillation. The polyfunctional organohydrogensiloxane produced by the above-described methods can be used, for example, as a crosslinker or co-crosslinker in hydrosilylation-curable compositions, such as release coating compositions.

[0041] Method for producing clustered functional organopolysiloxanes Alternatively, the above-described method may further comprise the step of functionalizing the multifunctional organohydrogensiloxane to form a clustered functional organopolysiloxane. Combining starting materials, the starting materials comprising: a) polyfunctional organohydrogensiloxanes, b) a hydrosilylation reaction catalyst, and The method may further include the step of combining starting material a) with a reactive species having, on average, at least one aliphatically unsaturated group per molecule capable of addition reacting with silicon-bonded hydrogen atoms of the polyfunctional organohydrogensiloxane, wherein starting material c) further comprises one or more curable groups per molecule. Briefly, this method can be carried out by modifying the method described in U.S. Pat. No. 9,593,209. Starting material a) described herein above can be combined with a reactive species and a hydrosilylation reaction catalyst (referred to as components c) and d, respectively) in the amounts and under the conditions described in U.S. Pat. No. 9,593,209, column 8, line 44 to column 10, line 47.

[0042] Starting material b) Hydrosilylation reaction catalyst In the method of functionalizing a multifunctional organohydrogensiloxane to form a clustered functional organopolysiloxane, suitable hydrosilylation catalysts for the starting material b) are known in the art and are commercially available.The hydrosilylation catalysts include platinum group metal catalysts.These hydrosilylation catalysts may be metals selected from platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the hydrosilylation catalyst may be a compound of such a metal, such as chloridetris(triphenylphosphane)rhodium(I) (Wilkinson's catalyst), a rhodium diphosphine chelate such as [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphosphino)ethane]dichlorodirhodium, chloroplatinic acid (Speier's catalyst), chloroplatinic acid hexahydrate, platinum dichloride, or a complex of such a compound with a low molecular weight organopolysiloxane or a platinum compound microencapsulated in a matrix or core-shell structure. Examples of complexes of platinum with a low molecular weight organopolysiloxane include a platinum complex of 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane (Karstedt's catalyst) and a platinum complex of methylvinylcyclosiloxane (Ashby's catalyst). These complexes may also be microencapsulated in a resin matrix. Alternatively, the hydrosilylation catalyst may comprise a platinum complex of 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane.Exemplary hydrosilylation catalysts are described in U.S. Patent Nos. 3,159,601, 3,220,972; 3,296,291; 3,419,593; 3,516,946; 3,814,730; 3,989,668; 4,784,879; 5,036,117 and 5,175,325, and European Patent No. 0347895(B).Microencapsulated hydrosilylation catalysts and their preparation methods are known in the art, as exemplified in U.S. Patent Nos. 4,766,176 and 5,017,654.The amount used can be sufficient to provide from 1 ppm to 1,000 ppm of platinum group metal, based on the combined weight of starting materials a), b), and c).

[0043] Starting material c) Reactive species The starting material c) reactive species described above for functionalizing the multifunctional organohydrogensiloxane to form the clustered functional organopolysiloxane is represented by the formula c-1), R 4 y SiR 5 (4-y) wherein the subscript y is 1 to 3, and each R 4 is an aliphatic unsaturated group capable of addition reaction, and each R 5 is an organic group having a curable functional group. Alternatively, the subscript y may be 1 to 2. Alternatively, the subscript y may be 1. Each R 4 may be independently selected from the group consisting of alkenyl (such as vinyl, allyl, and hexenyl) and alkynyl (such as propynyl or hexynyl). 5 may be independently selected from the group consisting of organic groups having an acrylate group, an alcohol group, an alkoxy group, an epoxy group, an isocyanate group, a methacrylate group, or a urethane group. 5 may be independently selected from the group consisting of an organic group having an acrylate group, an organic group having an epoxy group, and an organic group having a methacrylate group. 5 may be an organic group having an epoxy group. Suitable silanes are known in the art and are commercially available, for example, from Dow Silicones Corporation (Midland, Michigan, USA) or Gelest, Inc. Exemplary silanes include allyltrimethoxysilane, allyltriethoxysilane, or a combination thereof.

[0044] Alternatively, the starting material c) may be an organic compound that does not contain a silicon atom, such as a compound of formula c-2), R 6 R 7 [In the formula, each R 6is an aliphatic unsaturated group capable of addition reaction, and each R 7 is a curable group. 6 may be independently selected from the group consisting of alkenyl (such as vinyl, allyl, and hexenyl) and alkynyl (such as propynyl or hexynyl). 7 may be independently selected from the group consisting of organic groups having acrylate groups, alcohol groups, alkoxy groups, epoxy groups, isocyanate groups, methacrylate groups, and urethane groups. 7 may be selected from the group consisting of organic groups having acrylate groups, epoxy groups, and methacrylate groups. 7 may be an organic group having an epoxy group. Examples of suitable compounds of formula c-2) include allyl acrylate, allyl glycidyl ether, allyl methacrylate, and combinations thereof. Alternatively, c-2) may be allyl glycidyl ether. Alternatively, c-2) may be allyl methacrylate. Suitable compounds of formula c-2) are known in the art and are commercially available, for example, from Millipore Sigma (St. Louis, Missouri, USA).

[0045] The starting materials used in the method for producing the clustered functional organosiloxane may optionally further comprise one or more additional starting materials. The additional starting materials may be the additional components disclosed in U.S. Patent No. 9,593,209 (column 10, line 48 to column 16, line 17). The additional starting materials may be selected from the group consisting of fillers with or without treating agents, non-reactive resins, chain extenders, endblockers, and catalyst inhibitors.

[0046] In the above-described method, a') a product containing a clustered functional organopolysiloxane or a masterbatch of the clustered functional organopolysiloxane with a filler and / or a non-reactive resin is produced. The clustered functional organosiloxane has the general formula a'-1):

[0047] [ka] wherein the subscript v, the subscript n, R, and R 1 is as described above, and each R 8 are independently selected from the group consisting of H and curable groups, with the proviso that R 8 one or more of the formula a'-2):

[0048] [ka] [Wherein subscript n, subscript v, R, R 1 , and R 8 is as defined above], provided that at least one R 8 is a curable group. Alternatively, the clustered functional organosiloxane may have a unit of formula a'-3): [(R 8 RSiO 2 / 2 ) v-1 (-RSiO 2 / 2 )]2[O-(R 1 2SiO 2 / 2 ) n ] n’ [(R 8 RSiO 2 / 2 ) v-2 (-RSiO 2 / 2 )2] o’ wherein the subscripts v, n, n′, and o′ and the groups R, R 1 , and R 8 is as described above. Alternatively, R may occur 1 to 4 times in one molecule. 8 becomes a curing group (other than hydrogen). Alternatively, there are 1 to 3, or 1 to 2, or an average of 2 R in one molecule. 8 is a curing group (other than hydrogen). 8 The curable groups of R are derived from the starting material c) reactive species described above. 8 The curable group is R 4’ y SiR 5 (4-y) and R 6’ R 7 [In the formula, R4’ and R 6’ are divalent hydrocarbon radicals produced by the hydrosilylation reaction of the aliphatically unsaturated groups of starting material c) and the silicon-bonded hydrogen atoms of starting material a). Alternatively, subscript v may have an average value of 5, subscript n may have an average value of 10, subscript n' may be 1 to 2, and subscript o' may be 0 to 1. Alternatively, subscript v may be 5, subscript n may be 10, subscript n' may be 2, and subscript o' may be 1. Those skilled in the art will recognize that depending on various factors, such as the relative amounts of starting materials B) and C) used to prepare the organohydrogensiloxane, the product may contain two or more clustered functional organosiloxane species. The clustered functional organosiloxane may have an average of more than two cyclic moieties and more than two linear moieties per molecule (when o' > 0). Alternatively, if the subscript o'=0, then the product is of the formula a'-2),

[0049] [ka] [Wherein R and R 1 , R 8 and wherein subscript n and subscript v are as defined above.

[0050] The clustered functional organosiloxane may optionally be recovered from the product by any convenient means, such as stripping and / or distillation. The clustered functional organosiloxane prepared as described above can be used, for example, as an additive in adhesive compositions, such as thermal radical curable adhesive compositions.

[0051] Without being bound by theory, it is believed that a') the clustered functional organosiloxane can provide one or more of the following effects: 1) faster cure for the adhesive composition (when compared to an equivalent adhesive composition that does not contain a') above clustered functional organosiloxane); and 2) improved tensile and elongation properties of an adhesive prepared by curing the adhesive composition; and / or 3) improved crosslinkability of the adhesive composition.

[0052] curable composition The a) polyfunctional organohydrogensiloxane and the a') clustered functional organopolysiloxane are useful in curable compositions. (I) a polyfunctional organohydrogensiloxane, and / or a') a clustered functional organopolysiloxane; (II) a curing agent.

[0053] The curing agent selected will vary depending on the type and amount of curable substituents in the starting material (I). For example, when a) a polyfunctional organohydrogensiloxane is included in the curable composition, and / or when a') the clustered functional organosiloxane has SiH functional groups in addition to the curable groups introduced by starting material c) in the above-mentioned method, the curable substituents may be SiH. Alternatively, the curable substituents may be curable groups introduced by producing a') the clustered functional organosiloxane using the reactive species of starting material c) as described above.

[0054] For example, if starting material (I) has SiH functionality, (II) the curing agent may be a hydrosilylation reaction catalyst, as exemplified by those described above for starting material b) in the method for functionalizing a polyfunctional organohydrogensiloxane described above.

[0055] For example, if the starting material (I) includes a clustered functional organosiloxane having a radically curable group (e.g., an organic group having an epoxy, acrylate, or methacrylate functional group), the curing agent may include a radical initiator as the curing agent (II). The radical initiator may be a thermal radical initiator, a radiation-induced radical initiator, or a redox reagent. Thermal radical initiators include peroxides, which are known in the art and commercially available as disclosed in U.S. Pat. No. 9,593,209, column 16, line 49 to column 17, line 26. The thermal radical initiator may be used in an amount of 0.01 wt. % to 15 wt. %, alternatively 0.1 wt. % to 5 wt. %, alternatively 0.1 wt. % to 2 wt. %, based on the total weight of all starting materials in the curable composition.

[0056] Alternatively, the radical initiator may be a radiation photoinitiator. Radiation photoinitiators are known in the art and include cationic photoinitiators such as onium salts; radiation photoinitiators are disclosed in U.S. Pat. No. 9,593,209 at column 17, line 27 to column 18, line 40. Suitable radiation photoinitiators may be present in the curable composition in an amount of 0.01 wt. % to 15 wt. %, alternatively 0.1 wt. % to 10 wt. %, alternatively 0.1 wt. % to 5 wt. %, alternatively 0.1 wt. % to 2 wt. %, based on the total weight of all starting materials in the curable composition.

[0057] Alternatively, the radical initiator may be a redox reagent such as those disclosed in US Pat. No. 9,593,209, column 21, lines 33-53.

[0058] Alternatively, when the starting material (I) comprises a clustered functional organosiloxane having an organic group with an OH, alkoxy, or other hydrolyzable group, the curing agent (II) may comprise a condensation reaction catalyst in an amount of 0.001% to 5% by weight, based on the total weight of all starting materials in the curable composition. Exemplary condensation reaction catalysts are those disclosed in U.S. Pat. No. 9,593,209, column 18, line 41 to column 19, line 15.

[0059] Alternatively, when the starting material (I) includes a') a clustered functional organosiloxane, the curing agent (II) may include an organoborane amine complex. Suitable organoborane amine complexes are disclosed, for example, in U.S. Pat. No. 9,593,209, column 19, line 16 to column 21, line 33.

[0060] Alternatively, when the starting material (I) includes a clustered functional organosiloxane (a') having an organic group with an isocyanate or urethane functional group, the curing agent (II) may include a compound having two or more carbinol groups, such as a polyol, or an amine-functional compound. Examples of such curing agents are disclosed in column 21, lines 54 to 63.

[0061] Alternatively, when starting material (I) has two or more curable substituents, two or more curing agents can be used as starting material (II) in the curable composition. For example, a combination of a radical initiator and a condensation reaction catalyst can be used when starting material (I) has both radical curable groups and condensation reaction curable groups, such as epoxy and alkoxy. Alternatively, a combination of a hydrosilylation reaction catalyst and a condensation reaction catalyst can be used when starting material (I) has both SiH functional groups and condensation reaction curable groups, such as alkoxy.

[0062] The curable composition may optionally further comprise one or more additional starting materials. These are exemplified by (III) crosslinkers, (IV) solvents, (V) adhesion promoters, (VI) colorants, (VII) reactive diluents, (VIII) corrosion inhibitors, (IX) polymerization inhibitors, (X) fillers, (XI) filler treating agents, (XII) acid acceptors, and combinations thereof. Suitable additional starting materials are described and exemplified as other optional components in U.S. Pat. No. 9,592,209, column 22, line 5 to column 29, line 8. Other additional starting materials can be added. For example, the curable composition may optionally further comprise (XIII) reactive resins and polymers, (XIV) dual-cure compounds, or both. (XIII) reactive resins and polymers for the starting materials are known in the art; see, for example, U.S. Pat. No. 9,670,392, column 16, line 21 to column 18, line 35.

[0063] Thermally radically curable composition The curable composition may be a thermally radically curable composition.The thermally radically curable composition can be prepared as described in U.S. Pat. No. 9,670,392 by replacing the clustered functional organosiloxane described therein with the clustered functional organopolysiloxane prepared as described for starting material a') above.The thermally radically curable composition can be prepared by: (I) as starting material a'), the clustered functional organopolysiloxane described above, (II) a curing agent, (a) a radical initiator, and (b) a curing agent comprising a condensation reaction catalyst; (III) a crosslinking agent; (XIII) reactive resins and polymers.

[0064] The thermal radical curing composition may further comprise (XIV) a dual cure compound, which is an organosilicon compound having both hydrolyzable and free radical reactive groups, (VIII) a corrosion inhibitor, and (V) an adhesion promoter, all of whose starting materials are as described above.

[0065] adhesive composition Alternatively, the curable composition may be an adhesive composition. A) as starting material a'), a clustered functional organopolysiloxane as described above, which has acrylate, epoxy and / or methacrylate functional groups, B) reactive resins and polymers; C) a condensation reaction catalyst; D) a free radical initiator.

[0066] Starting Materials B) Reactive Resins and Polymers The starting material B) in the adhesive composition is a reactive resin and polymer. The reactive resin and polymer may be the reactive resin and polymer (XIII) described above as a starting material, see U.S. Patent No. 9,670,392. Alternatively, the reactive resin and polymer may be a polyalkoxy end-capped resin-polymer blend prepared as described in U.S. Provisional Patent Application No. 62 / 548,558, filed August 22, 2017. The polyalkoxy end-capped resin-polymer blend may be: i) Formula, (R 2’ 3SiO 1 / 2 ) and (SiO 4 / 2 )[where each R 2’ are independently monovalent hydrocarbon groups, provided that at least one R 2’ (R has aliphatic unsaturation) 2’ 3SiO 1 / 2 ) units (M units), (SiO 4 / 2 a siloxane resin having a molar ratio (M:Q ratio) of 0.5:1 to 1.5:1 of siloxane units (Q units); ii) Formula, (R 2’ 3SiO 1 / 2 ) ii and (R 2’ 2SiO 2 / 2 ) hh(D units), wherein the subscript hh is 20 to 1000, and the subscript ii has an average value of 2; and iii) an alkoxy-functional organohydrogensiloxane oligomer having the unit formula:

[0067] [ka] (HR 22 2SiO 1 / 2 ) ppp (R 22 3SiO 1 / 2 ) qqq (HR 22 SiO 2 / 2 ) rrr (R 22 2SiO 2 / 2 ) sss (R 22 SiO 3 / 2 ) ttt (HSiO 3 / 2 ) uuu (SiO 4 / 2 ) kk [In the formula, each D 1 each independently represents a divalent hydrocarbon group having 2 to 18 carbon atoms, and each R 22 are independently a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 18 carbon atoms (R 1 (such as those described above for R 23 are independently monovalent hydrocarbon groups (R 1 the subscript nnn is 0 or 1, the subscript ooo is 0, the subscripts qqq, sss, and ttt are such that 5≧qqq≧0, 5≧sss≧0, the subscript ttt is 0 or 1, the subscript kk is 0 or 1, the subscript nnn>0, and have values ​​such that the quantity (mmm+ppp+qqq+rrr+sss+ttt+uuu+kk)≦50, with the proviso that 1 an alkoxy-functional organohydrogensiloxane oligomer having >90 mole % of the groups being linear; iv) A polyalkoxy end-capped resin-polymer blend comprising the reaction product of a hydrosilylation catalyst and 1 is an alkylene group, such as ethylene, propylene, butylene, or hexylene; an arylene group, such as phenylene; or an alkylarylene group, such as

[0068] [ka] Alternatively, each D 1 is an alkylene group such as ethylene or propylene, or ethylene.

[0069] Starting material C) Condensation reaction catalyst The starting material C) in the adhesive composition described above is a condensation catalyst. The condensation catalyst may be selected from conventional condensation catalysts effective in silanol-silanol condensation reactions, including organometallic compounds, amines, and a wide range of organic and inorganic bases and acids. Organometallic compounds include tin, titanium, zinc, zirconium, hafnium, and other organic compounds. The condensation catalyst may also be an organotin compound or an organotitanium compound. Exemplary organotin compounds include i) dibutyltin dilaurate, ii) dimethyltin dilaurate, iii) di-(n-butyl)tin bisketonate, iv) dibutyltin diacetate, v) dibutyltin maleate, vi) dibutyltin diacetylacetonate, vii) dibutyltin dimethoxide, viii) dibutyltin dioctanoate, ix) dibutyltin diformate, x) dimethyltin dibutyrate, xi) dimethyltin dineodecanoate, xii) dibutyltin dineodecanoate, xiii) triethyltin tartrate, xiv) dibutyltin dibenzoate, xv) butyltin tri-2-ethylhexanoate, xvi) dioctyltin diacetate, xvii) stannous octylate, xix) stannous butyrate, xx) tin naphthenate, xxi) dimethyltin dichloride, xxii) tin(II) diacetate, xxiii) tin(II) dioctanoate, xxiv) tin(II) diethylhexanoate, xxv) tin(II) dilaurate, such as xxvi) stannous octoate, xxvii) stannous oleate, xxviii) stannous acetate, xxix) stannous laurate, xxx) stannous stearate, xxxi) stannous hexanoate, xxxii) stannous succinate, xxxiii) stannous caprylate, and xxxiv) combinations of two or more of i) to xxxiii).Exemplary organotitanium compounds may be selected from the group consisting of i) tetra-n-butyl titanate, ii) tetraisopropyl titanate, iii) tetra-t-butyl titanate, iv) tetrakis(2-ethylhexyl) titanate, v) acetylacetonate titanate chelate, vi) ethyl acetoacetate titanate chelate, vii) triethanolamine titanate chelate, viii) tri-n-butyl titanate, and ix) combinations of two or more of i), ii), iii), iv), v), vi), vii), and viii).

[0070] The amount of condensation reaction catalyst in the adhesive composition will vary depending on various factors, such as the selection of other starting materials, whether any additional starting materials are added, and the end use of the adhesive composition. However, the condensation reaction catalyst may be present in an amount ranging from 0.01% to 25% by weight, based on the total weight of all starting materials in the adhesive composition. Alternatively, the condensation reaction catalyst may be present in an amount of 0.1% to 25%, alternatively 0.1% to 15%, alternatively 0.5% to 15%, alternatively 0.5% to 10%, or alternatively 0.1% to 5%.

[0071] Starting Material D) Free Radical Initiator The starting material D) in the adhesive composition described above is a free radical initiator. The free radical initiator may include an azo compound or an organic peroxide compound. Suitable azo compounds include azobenzene, azobenzene-p-sulfonic acid, azobisdimethylvaleronitrile, azobisisobutyronitrile, and combinations thereof. Suitable organic peroxide compounds include dialkyl peroxides, diaryl peroxides, diacyl peroxides, alkyl hydroperoxides, and aryl hydroperoxides. Specific organic peroxide compounds are as described above for starting material (II). Alternatively, the organic peroxide may be exemplified by benzoyl peroxide; dibenzoyl peroxide; 4-monochlorobenzoyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butylcumyl peroxide, tert-butyloxide 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,4-dichlorobenzoyl peroxide, di-tert-butylperoxy-diisopropylbenzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-di-tert-butylperoxyhexane-3,2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, or a combination of two or more thereof.

[0072] The amount of free radical initiator added to the adhesive composition will vary depending on various factors, such as the type and amount of condensation reaction catalyst selected and the selection of other starting materials in the adhesive composition, but the free radical initiator may be present in an amount of 0.1 wt % to 5 wt %, alternatively 0.2 wt % to 3 wt %, alternatively 0.5 wt % to 2 wt %, based on the total weight of all starting materials in the adhesive composition.

[0073] Additional Starting Materials in the Adhesive Composition The adhesive compositions described above may further comprise one or more additional starting materials (different from, and added in addition to, the above-described starting materials A), B), C), and D). The additional starting materials may be selected from the group consisting of E) dual cure compounds, F) adhesion promoters, G) corrosion inhibitors, H) rheology modifiers, I) driers, J) crosslinkers, K) fillers, L) spacers, M) acid scavengers, N) silanol-functional polydiorganosiloxanes, O) fluorescent optical brighteners, P) chain transfer agents, Q) (meth)acrylate monomers, R) polyalkoxy-terminated polydiorganosiloxanes, S) colorants, and two or more of E), F), G), H), I), J), K), L), M), N), O), P), Q), R), and S).

[0074] Starting Material E) Dual Cure Compound The adhesive composition described above may optionally further comprise starting material E) a dual-cure compound. The dual-cure compound is an organosilicon compound having at least one hydrolyzable group and at least one free-radical reactive group in one molecule. The organosilicon compound starting material E) has the formula: 14 mm R 22 nn Six 4-(mm+nn) [In the formula, R 22 is as described above, and R 14 is a curable group (such as an acrylate, epoxy, or methacrylate functional group), X is a hydrolyzable group, the subscript mm is 1-2, the subscript nn is 0-2, and the quantity (mm+nn) is 2-3.

[0075] Each X independently represents a hydrolyzable group that may be selected from acetamido, acyloxy, such as acetoxy, alkoxy, amido, amino, aminoxy, oximo, ketoximo, and methylacetamido. X is not a hydroxyl group. Alternatively, each X may be an acetoxy or alkoxy group. Alternatively, each X is an alkoxy group, such as methoxy, ethoxy, propoxy, or butoxy, or is methoxy.

[0076] Alternatively, the organosilicon compound of starting material E) may have the unit formula: (X mm R 22 (3-mm) SiO 1 / 2 ) oo (R 14 R 22 2SiO 1 / 2 ) pp (R 22 2SiO 2 / 2 ) qq (R 22 XSiO 2 / 2 ) rr (R 14 R 22 SiO 2 / 2 ) ss (R 14 SiO 3 / 2 ) ww (R 22 SiO 3 / 2 ) tt (SiO 4 / 2 ) uu [In the formula, R 22 , R 14wherein x, y, y, y, z, z, z are as defined above, and the polyorganosiloxane may include polyorganosiloxanes of the following formula:

[0000] ,

[0000] ,

[0000] ,

[0000] ,

[0000] , and

[0000] , and the subscripts oo, pp, qq, rr, ss, ww, tt, uu, and uu are as defined above, and the subscripts oo ... Alternatively, the subscript qq is 0 to 1,000, or 0 to 500, or 0 to 200, or 0 to 100, or 1 to 500, or 1 to 200, or 1 to 100. Alternatively, the subscript rr is 0 to 100, or 0 to 50, or 0 to 20, or 0 to 10, or 1 to 50, or 1 to 20, or 1 to 10. Alternatively, the subscript ss is 0 to 100, or 0 to 50, or 0 to 20, or 0 to 10, or 1 to 50, or 1 to 20, or 1 to 10. Alternatively, the subscript ww is 0 to 100, or 0 to 50, or 0 to 20, or 0 to 10, or 1 to 50, or 1 to 20, or 1 to 10. Alternatively, the subscript tt is 0 to 1,000, or 0 to 500, or 0 to 200, or 0 to 100, or 1 to 500, or 1 to 200, or 1 to 100. Alternatively, the subscript uu is 0 to 1,000, or 0 to 500, or 0 to 200, or 0 to 100, or 1 to 500, or 1 to 200, or 1 to 100.

[0077] Examples of starting materials E) include silanes such as methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, acryloxypropylmethyldimethoxysilane, acryloxypropyldimethylmethoxysilane, and methacryloxypropyldimethylmethoxysilane.

[0078] The amount of dual-cure compound in the adhesive composition will vary depending on various factors, such as the selection of other starting materials, whether any additional starting materials are added, and the end use of the composition. However, the dual-cure compound may be present in an amount ranging from 0.01% to 25% by weight, based on the total weight of all starting materials in the adhesive composition. Alternatively, the dual-cure compound may be present in an amount of 0.1% to 25%, alternatively 0.1% to 15%, alternatively 0.5% to 15%, alternatively 0.5% to 10%, or alternatively 0.1% to 5%.

[0079] Starting Material F) Adhesion Promoter The adhesive composition described above may optionally further comprise F) an adhesion promoter. Suitable adhesion promoters may include transition metal chelates, hydrocarbonoxysilanes, e.g., alkoxysilanes, combinations of alkoxysilanes with hydroxy-functional polyorganosiloxanes, amino-functional silanes, or combinations thereof. The adhesion promoter may be a compound represented by the formula: R 15 aaa R 16 bbb Si(OR 17 ) 4-(aaa+bbb) [In the formula, each R 15 are independently monovalent organic groups having at least 3 carbon atoms, and R 16 contains at least one SiC-bonding substituent having an adhesion-promoting group such as an amino group, an epoxy group, a mercapto group, or an acrylate group; 17are independently a saturated hydrocarbon group, such as an alkyl group, having 1 to 4 carbon atoms; the subscript aaa has a value ranging from 0 to 2; and the subscript bbb is either 1 or 2, with the quantity (aaa + bbb) being 3 or less. Alternatively, the adhesion promoter may comprise a partial condensate of the above-mentioned silane. Alternatively, the adhesion promoter may comprise a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane, such as trimethoxysilyl-terminated polydimethylsiloxane, which is commercially available from Dow Silicones Corporation (Midland, Michigan, USA).

[0080] Alternatively, the adhesion promoter may comprise an unsaturated or epoxy-functional compound. The adhesion promoter may comprise an unsaturated or epoxy-functional alkoxysilane. For example, the functional alkoxysilane may be of the formula: R 18 ccc Si(OR 19 ) (4-ccc) wherein the subscript ccc is 1, 2, or 3, or the subscript ccc is 1. Each R 18 is at least one R 18 is independently a monovalent organic group, provided that R is an unsaturated organic group or an epoxy-functional organic group. 18 Epoxy-functional organic groups of R are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. 18 The unsaturated organic groups are exemplified by 3-methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecylenyl, and the like. 19 are independently saturated hydrocarbon groups having 1 to 4 carbon atoms or 1 to 2 carbon atoms. 19 is exemplified by methyl, ethyl, propyl, and butyl.

[0081] Examples of suitable epoxy-functional alkoxysilanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane, (epoxycyclohexyl)ethyltrimethoxysilane, (epoxycyclohexyl)ethyltriethoxysilane, and combinations thereof. Examples of suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and combinations thereof.

[0082] Alternatively, the adhesion promoter may comprise an epoxy-functional siloxane, such as the reaction product of a hydroxy-terminated polyorganosiloxane and an epoxy-functional alkoxysilane, as described above, or a physical blend of a hydroxy-terminated polyorganosiloxane and an epoxy-functional alkoxysilane. The adhesion promoter may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane. For example, the adhesion promoter may be exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane with a reaction product of a hydroxy-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane, a mixture of 3-glycidoxypropyltrimethoxysilane with a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane with a hydroxy-terminated methylvinylsiloxane / dimethylsiloxane copolymer.

[0083] Alternatively, the adhesion promoter may be H2N(CH2)2Si(OCH3)3, H2N(CH2)2Si(OCH2CH3)3, H2N(CH2)3Si(OCH3)3, H2N(CH2)3Si(OCH2CH3)3, 2)3Si(OCH3)3, CH3NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)5Si(OCH3)3, CH3NH(CH2)5Si(OCH2CH3)3, H2N(CH2)2NH(CH2)3Si( OCH3)3, H2N(CH2)2NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH2CH3)3, C4H9 NH(CH2)2NH(CH2)3Si(OCH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH2CH3)3, H2N(CH2)2SiCH3(OCH3)2, H2N(CH2)2SiCH3(OCH2CH 3)2, H2N(CH2)3SiCH3(OCH3)2, H2N(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)5SiCH3(OCH3)2, CH3NH(CH2)5SiCH3(OCH2CH3)2, H2N(CH2)2NH(CH2)3SiCH3(OCH3)2, H2N(CH2)2NH(CH2)3SiCH The silanes may include amino-functional silanes such as amino-functional alkoxysilanes exemplified by C4H9NH(CH2)2NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, and combinations of two or more thereof.

[0084] Alternatively, the adhesion promoter may comprise a transition metal chelate. Suitable transition metal chelates include titanates, zirconates such as zirconium acetylacetonate, aluminum chelates such as aluminum acetylacetonate, and combinations thereof.

[0085] Alternatively, the adhesion promoter may comprise a triazine-based compound having a functional group reactive with starting material A), starting material B), or, if present, starting material E), or two or more thereof. The triazine ring may be mono-, di-, or tri-substituted, with at least one of the substituents being a reactive functional group. The functional group may be free-radical reactive or condensation reactive. Examples of triazine compounds having free-radical reactive functional groups include triallyl isocyanurate, diallylpropyl isocyanurate, tri-(methacryloxypropyl)isocyanurate, triallyloxytriazine, trimethacryloxytriazine, triacryloylhexahydrotriazine, and tris[2-(acryloyloxy)ethyl]isocyanurate. Examples of triazine compounds having condensation reactive groups include 2,4,6-tris(methyldimethoxysilyl)triazine and tris[3-(trimethoxysilyl)propyl]isocyanurate.

[0086] The exact amount of adhesion promoter will vary depending on various factors, such as the selection and amounts of other starting materials in the adhesive composition. However, when present, the adhesion promoter can be added to the adhesive composition in an amount of 0.01 to 50 parts by weight, alternatively 0.01 to 10 parts by weight, alternatively 0.01 to 5 parts by weight, based on the total weight of all starting materials in the adhesive composition. Examples of suitable adhesion promoters are described in U.S. Patent No. 9,156,948.

[0087] Starting Material G) Corrosion Inhibitor The adhesive composition may optionally further comprise starting material G) a corrosion inhibitor. Examples of suitable corrosion inhibitors include benzotriazole, mercaptobenzothiazole, and commercially available corrosion inhibitors such as 2-mercaptobenzothiazole from Millipore Sigma, and 2,5-dimercapto-1,3,4-thiadiazole derivative (CUVAN™ 826) and alkyl thiadiazole (CUVAN™ 484) from R.T. Vanderbilt (Norwalk, Connecticut, USA). Examples of suitable corrosion inhibitors are exemplified by those described in U.S. Pat. No. 9,156,948. When present, the amount of corrosion inhibitor may be 0.05% to 0.5% by weight, based on the total weight of all starting materials in the adhesive composition.

[0088] Starting Materials H) Rheology Modifiers The adhesive composition may optionally further comprise up to 5 wt. %, alternatively 1 wt. 2 wt. %, of a starting material H) rheology modifier, based on the total weight of all starting materials in the composition. Rheology modifiers are commercially available. Examples of suitable rheology modifiers include polyamides, hydrogenated castor oil derivatives, metal soaps, microcrystalline waxes, and combinations thereof. Examples of suitable rheology modifiers are exemplified by those described in U.S. Pat. No. 9,156,948. The amount of rheology modifier will vary depending on various factors, including the specific rheology modifier selected and the selection of other starting materials used in the composition. However, the amount of rheology modifier may range from 0 to 20 wt. %, alternatively 1 to 15 wt. %, alternatively 1 to 5 wt. % based on the total weight of all starting materials in the adhesive composition.

[0089] Starting Materials I) Desiccant The above-described composition may optionally further comprise a starting material I) a desiccant. The desiccant captures water from various sources. For example, the desiccant can capture by-products of the condensation reaction, such as water and alcohol. Examples of suitable desiccants are disclosed, for example, in U.S. Pat. No. 9,156,948. Examples of adsorbents suitable for the desiccant include inorganic particulates, such as zeolites, such as chabazite, mordenite, and analcite; alkali metal aluminosilicates; silica gel; silica-magnesia gel; activated carbon; activated alumina; calcium oxide; and molecular sieves, such as combinations thereof. The adsorbent may have a particle size of 10 μm or less. The adsorbent may have an average pore size, for example, 10 Å (angstroms) or less, sufficient to adsorb water and alcohol.

[0090] Alternatively, the desiccant can trap water and / or other by-products by chemical means. The amount of silane crosslinker added to the composition (in addition to any silane crosslinker used as starting material J) can function as a chemical desiccant. Without being bound by theory, it is believed that a chemical desiccant can be added to the dry part of a multi-part composition to protect the composition from water after the parts are mixed together. For example, alkoxysilanes suitable as desiccants include vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, isobutyltrimethoxysilane, and combinations thereof. The amount of desiccant will vary depending on the particular desiccant selected. However, when starting material I) is a chemical desiccant, the amount may range from 0 to 15 parts by weight, alternatively from 0 to 10 parts by weight, alternatively from 0 to 5 parts by weight, alternatively from 0 to 0.5 parts by weight, based on the total weight of all starting materials in the composition.

[0091] Starting Material J) - Crosslinker The above-described compositions may optionally further comprise starting material J) a crosslinker. The crosslinker may comprise a silane crosslinker having hydrolyzable groups, or a partial or complete hydrolysis product thereof. The crosslinker has, on average, more than two substituents per molecule that are reactive with the hydrolyzable groups of starting material B). Examples of suitable silane crosslinkers are those having the general formula R 20 ddd Si(R 21 ) (4-ddd) [In the formula, each R 20 are independently a monovalent hydrocarbon group such as an alkyl group; 21 is a hydrolyzable substituent, which may be the same group as X described above. Alternatively, each R 21 may be, for example, a hydrogen atom, a halogen atom, an acetamido group, an acyloxy group such as acetoxy, an alkoxy group, an amido group, an amino group, an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, or a methylacetamido group, and each instance of the subscript ii may be 0, 1, 2, or 3. For silane crosslinkers, the subscript ddd has an average value greater than 2. Alternatively, the subscript ddd may have a value ranging from 3 to 4. Alternatively, each R 21 may be independently selected from hydroxyl, alkoxy, acetoxy, amide, or oxime. Alternatively, the silane crosslinker may be selected from acyloxysilanes, alkoxysilanes, ketoximosilanes, and oximosilanes.

[0092] The silane crosslinker may include an alkoxysilane, such as a dialkoxysilane, such as a dialkyldialkoxysilane; a trialkoxysilane, such as an alkyltrialkoxysilane; a tetraalkoxysilane; or a partial or complete hydrolysis product thereof, or another combination thereof. Examples of suitable trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, and combinations thereof, or methyltrimethoxysilane. Examples of suitable tetraalkoxysilanes include tetraethoxysilane. Alternatively, the silane crosslinker may include an acyloxysilane, such as acetoxysilane. Examples of acetoxysilanes include tetraacetoxysilane, organotriacetoxysilane, diorganodiacetoxysilane, or combinations thereof. Exemplary acetoxysilanes include, but are not limited to, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, propyltriacetoxysilane, butyltriacetoxysilane, phenyltriacetoxysilane, octyltriacetoxysilane, dimethyldiacetoxysilane, phenylmethyldiacetoxysilane, vinylmethyldiacetoxysilane, diphenyldiacetoxysilane, tetraacetoxysilane, and combinations thereof. Alternatively, the crosslinker may comprise an organotriacetoxysilane, such as a mixture comprising methyltriacetoxysilane and ethyltriacetoxysilane. Examples of suitable silanes for starting material J) containing both alkoxy and acetoxy groups that can be used in the composition include methyldiacetoxymethoxysilane, methylacetoxydimethoxysilane, vinyldiacetoxymethoxysilane, vinylacetoxydimethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydiethoxysilane, and combinations thereof.

[0093] Alternatively, the crosslinker may be H2N(CH2)2Si(OCH3)3, H2N(CH2)2Si(OCH2CH3)3, H2N(CH2)3Si(OCH3)3, H2N(CH2)3Si(OCH2CH3)3, CH3NH(CH2)3Si(OCH3)3, CH3NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)5Si(OCH3)3, CH3NH(CH2)5Si(OCH2CH3)3, H2N(CH2)2NH(CH 2)3Si(OCH3)3, H2N(CH2)2NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH2 CH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH2CH3)3, H2N(CH2)2SiCH3(OCH3)2, H2N(CH2 )2SiCH3(OCH2CH3)2, H2N(CH2)3SiCH3(OCH3)2, H2N(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2 )3SiCH3(OCH2CH3)2, CH3NH(CH2)5SiCH3(OCH3)2, CH3NH(CH2)5SiCH3(OCH2CH3)2, H2N(CH2)2NH(CH2)3SiCH3(OCH3)2 , HN(CH)NH(CH)SiCH(OCHCH), CHNH(CH)NH(CH)SiCH(OCH), CHNH(CH)NH(CH)SiCH(OCH), CHNH(CH)NH(CH)SiCH(OCH), CHNH(CH)NH(CH)SiCH(OCH), CHNH(CH)NH(CH)SiCH(OCH), or combinations thereof. Examples of suitable silane crosslinkers are disclosed in U.S. Pat. No. 9,156,948.

[0094] Alternatively, the crosslinker may comprise a multifunctional (meth)acrylate crosslinker, such as, for example, a di(meth)acrylate, exemplified by ethylene glycol dimethacrylate, ethylene glycol diacrylate, triethylene glycol dimethacrylate, diethylene glycol bismethacryloxycarbonate, polyethylene glycol diacrylate, tetraethylene glycol dimethacrylate, diglycerol diacrylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triglycidyl ether, trimethylolpropane tris(2-methyl-1-aziridine)propionate, trimethylolpropane trimethacrylate, acrylate-tipped urethane-containing prepolymers, polyether diacrylates, and dimethacrylates, as well as combinations of two or more thereof. Suitable multifunctional (meth)acrylate crosslinkers are disclosed, for example, in U.S. Pat. No. 8,304,543, column 11, lines 46-65.

[0095] When present, the crosslinker may be added in an amount ranging from 0.1% to 10% by weight, based on the total weight of all starting materials in the adhesive composition.

[0096] Starting Material K) Filler The above-described compositions may optionally further comprise a filler (K). The filler may comprise a reinforcing filler, an extending filler, a conductive filler, or a combination thereof. For example, the compositions may optionally further comprise a starting material (K1) reinforcing filler, which, if present, may be added in an amount of 0.1% to 95% by weight, or alternatively 1% to 60% by weight, based on the total weight of all starting materials in the adhesive composition. The exact amount of starting material (K1) will vary depending on various factors, such as the form of the reaction product of the composition and whether other fillers are added. Examples of suitable reinforcing fillers include reinforcing silica fillers (e.g., fumed silica, silica aerogel, silica xerogel, and precipitated silica). Fumed silica is known in the art and commercially available, such as the fumed silica sold under the name CAB-O-SIL by Cabot Corporation (Massachusetts, USA).

[0097] The adhesive composition may optionally further comprise a starting material (K2) extending filler in an amount ranging from 0.1% to 95% by weight, alternatively from 1% to 60% by weight, alternatively from 1% to 20% by weight, based on the total weight of all starting materials in the adhesive composition. Examples of extending fillers include crushed quartz, aluminum oxide, magnesium oxide, calcium carbonate (e.g., precipitated calcium carbonate), zinc oxide, talc, diatomaceous earth, iron oxide, clay, mica, chalk, titanium dioxide, zirconia, sand, carbon black, graphite, or combinations thereof. Extending fillers are known in the art and commercially available, such as ground silica sold under the name MIN-U-SIL by US Silica (Berkeley Springs, WV). Suitable precipitated calcium carbonates include Winnofil™ SPM manufactured by Solvay, and Ultrapflex™ and Ultrapflex™ 100 manufactured by SMI. Examples of suitable fillers are disclosed in US Pat. No. 9,156,948.

[0098] Starting material L) spacer The adhesive composition described above may optionally further comprise a spacer (L). The spacer may comprise organic particles, inorganic particles, or a combination thereof. The spacer may be thermally conductive, electrically conductive, or both. The spacer may have a desired particle size, for example, a particle size ranging from 25 μm to 125 μm. The spacer may comprise monodisperse beads such as glass or polymer (e.g., polystyrene) beads. The spacer may comprise a thermally conductive filler such as alumina, aluminum nitride, atomized metal powder, boron nitride, copper, and silver. The amount of spacer varies depending on various factors, such as particle size distribution, the pressure applied during use of the composition prepared by mixing the components or the cured product prepared therefrom, the temperature during use, and the desired thickness of the mixed composition or the cured product prepared therefrom. However, the composition may contain the spacer in an amount of 0.05 wt % to 2 wt %, or alternatively 0.1 wt % to 1 wt %, based on the total weight of all starting materials in the composition.

[0099] Starting Material M) Acid Scavenger The above-described compositions may optionally further comprise M) an acid scavenger. Suitable acid scavengers include various inorganic and organic compounds that are basic in nature, such as magnesium oxide, calcium oxide, and combinations thereof. The composition may comprise 0% to 10% by weight of the acid scavenger, based on the total weight of all starting materials in the composition.

[0100] Starting Material N) Silanol-functional Polydiorganosiloxane The above-described composition may optionally further comprise N) a silanol-functional polydiorganosiloxane. The starting material N) is a silanol-functional polydiorganosiloxane of the formula: HOR 22 2SiO(R 22 2SiO) eee ((HO)R 22 SiO) fff SiR 22 2OH or formula, R3SiO(R2SiO) ggg ((HO)RSiO) hhh SiR3[wherein, R 22are as described above], or combinations thereof. The subscript eee may be zero or a positive number. Alternatively, the subscript eee has an average value of at least 2. Alternatively, the subscript eee may be from 2 to 2000. The subscript fff may be zero or a positive number. Alternatively, the subscript fff may have an average value of 0 to 2000. The subscript ggg may be zero or a positive number. Alternatively, the subscript ggg may have an average value of 0 to 2000. The subscript hhh has an average value of at least 2. Alternatively, the subscript hhh may have an average value in the range of 2 to 2000.

[0101] Starting materials N) are polydiorganosiloxanes, e.g. i) hydroxy-terminated polydimethylsiloxane; ii) hydroxy-terminated poly(dimethylsiloxane / methylphenylsiloxane); iii) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydroxysiloxane), and iv) may include a combination of two or more of i), ii), and iii).

[0102] Hydroxyl-endblocked polydiorganosiloxanes suitable for use as starting material N) can be prepared by methods known in the art, such as the hydrolysis and condensation of the corresponding organohalosilanes or the equilibration of cyclic polydiorganosiloxanes. When added to the adhesive composition, starting material N) may be present in an amount of 0.1 wt % to 20 wt %, alternatively 0.1 wt % to 10 wt %, alternatively 0.1 wt % to 5 wt %, based on the total weight of all starting materials in the adhesive composition.

[0103] Starting Materials O) Optical Brighteners The adhesive compositions described above may optionally further comprise starting material O) an optical brightener. Suitable optical brighteners are commercially available, such as 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole), commercially available as TINOPAL™ OB. When added to the composition, the optical brightener may be present in an amount of 0.1% to 2% by weight, based on the total weight of all starting materials in the adhesive composition.

[0104] Starting material P) Chain transfer agent The adhesive compositions described above may optionally further comprise P) a chain transfer agent. When added to the adhesive composition, the chain transfer agent may be present in an amount of 0.01 wt % to 5 wt %, alternatively 0.01 wt % to 2 wt %, alternatively 0.1 wt % to 2 wt %, based on the total weight of all starting materials in the composition.

[0105] Starting Material Q) (Meth)acrylate Monomer The adhesive composition described above may optionally further comprise starting material Q) a (meth)acrylate monomer. (Meth)acrylate monomers are exemplified by methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, cyclohexylmethyl acrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, and cyclohexyl methacrylate. When added to the adhesive composition, the (meth)acrylate monomer may be present in an amount of 0.1 wt % to 35 wt %, alternatively 0.1 wt % to 25 wt %, alternatively 0.1 wt % to 15 wt %, alternatively 0.1 wt % to 10 wt %, based on the total weight of all starting materials in the adhesive composition.

[0106] Starting Material R) Polyalkoxy-Terminated Polydiorganosiloxane Starting material R) is a polyalkoxy-terminated polydiorganosiloxane in addition to any prepared by the preparation of starting material B) described above. Starting material R) may be a polyalkoxy-terminated polydiorganosiloxane prepared as described above for starting material B), except that it does not contain a siloxane resin. Alternatively, starting material R) may be a polyalkoxy-terminated polydiorganosiloxane prepared by a platinum-catalyzed hydrosilylation reaction.

[0107] Starting material S) colorant The adhesive composition described above may optionally further comprise starting material S) a colorant, which may be a dye or a pigment such as carbon black.

[0108] When selecting starting materials for the adhesive composition described above, certain starting materials described herein may have more than one function, and therefore the types of starting materials may overlap. For example, certain alkoxysilanes may be useful as crosslinkers and / or adhesion promoters and / or desiccants. Certain particles may be useful as fillers and spacers. When starting materials are added to the adhesive composition, the additional starting materials differ from each other.

[0109] Method for preparing adhesive composition The adhesive composition described above can be prepared by 1) combining starting materials B)i) an organosiloxane resin and B)ii) a polydiorganosiloxane to form a resin polymer blend (RPB). A solvent can optionally be used to homogenize the RPB. One or more of the starting materials, such as the organosiloxane resin, can be dissolved or dispersed in a solvent such as those mentioned above, for example, an aromatic hydrocarbon such as benzene, toluene, or xylene. The amount of solvent can be 0% to 60% by weight, alternatively 10% to 50% by weight, or alternatively 20% to 40% by weight, based on the total weight of all starting materials in the adhesive composition. As described above, starting materials B)iii) and B)iv) can be combined with the RPB to form a converted RPB. The method may further include 2) combining the converted RPB and starting materials A), C), and D) by any convenient means, such as mixing. One or more additional starting materials E)-S), as described above, can be added during step 1), step 2), or both. The starting materials can be combined at 20°C to 150°C. The process can further include heating the starting materials in step 1), step 2), or both, at a temperature of 50°C to 150°C, or alternatively, 60°C to 120°C. Pressure is not critical; the process can be carried out at ambient pressure.

[0110] Release Coating Composition Alternatively, the curable composition may be a release coating composition. (i) a polyfunctional organohydrogensiloxane prepared by the method described above; (ii) a polyorganosiloxane capable of undergoing a hydrosilylation reaction and having an average of at least two silicon-bonded aliphatic unsaturated groups per molecule; (iii) a hydrosilylation reaction catalyst; and (iv) a hydrosilylation reaction inhibitor.

[0111] Starting material (ii) polyorganosiloxane having an aliphatic unsaturated group The starting material (ii) in the release coating composition is a polyorganosiloxane having on average at least two silicon-bonded aliphatic unsaturated groups per molecule capable of undergoing a hydrosilylation reaction, or a polyorganosiloxane having on average at least two silicon-bonded groups per molecule having terminal aliphatic unsaturation. This polyorganosiloxane may be linear, branched, partially branched, cyclic, resinous (i.e., having a three-dimensional network), or may contain a combination of different structures. The polyorganosiloxane has an average formula, R 13 a SiO (4-a) / 2 [wherein each R 13 is independently selected from monovalent hydrocarbon groups or monovalent halogenated hydrocarbon groups, provided that in each molecule, at least two of the R 13 contain aliphatic unsaturation, and the subscript a is selected such that 0 < a ≦ 3.2]. It may have. Suitable monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups for R 13 are as described above for R 1 . The above average formula of the polyorganosiloxane is alternatively (R 13 3SiO 1 / 2 ) b (R 13 2SiO 2 / 2 ) c (R 13 SiO 3 / 2 ) d (SiO 4 / 2 ) e [wherein R 13are defined above, and the subscripts b, c, d, and e are each independently ≧0 to ≦1, with the proviso that the quantity (b+c+d+e)=1. One of ordinary skill in the art will understand how such M, D, T, and Q units and their mole fractions affect the subscript a in the above average formula. T units (denoted by subscript d), Q units (denoted by subscript e), or both, are typically present in the polyorganosiloxane resin, while D units, denoted by subscript c, are typically present in the polyorganosiloxane polymer (and may also be present in the polyorganosiloxane resin or branched polyorganosiloxane).

[0112] Alternatively, starting material (i) may comprise a substantially linear, or linear, polyorganosiloxane. The substantially linear polyorganosiloxane may have the average formula R 13 a’ SiO (4-a’) / 2 [In the formula, each R 13 is as defined above, and the subscript a' is selected so that 1.9≦a'≦2.2.

[0113] At room temperature, the substantially linear polyorganosiloxane may be a flowable liquid or may have the form of an uncured rubber. The substantially linear polyorganosiloxane may have a viscosity at 25°C of 10 mPa·s to 30,000,000 mPa·s, alternatively 10 mPa·s to 10,000 mPa·s, alternatively 100 mPa·s to 1,000,000 mPa·s, alternatively 100 mPa·s to 100,000 mPa·s. Viscosity can be measured at room temperature using a Brookfield LV DV-E viscometer, i.e., RV-1 through RV-7, equipped with a spindle appropriately selected for the viscosity of the substantially linear polyorganosiloxane.

[0114] Alternatively, (ii) when the polyorganosiloxane is substantially linear or linear, the polyorganosiloxane has an average unit formula: (R 10 R 92SiO 1 / 2 ) aa (R 10 R 9 SiO 2 / 2 ) bb (R 10 2SiO 2 / 2 ) cc (R 9 3SiO 1 / 2 ) dd [In the formula, each R 9 are independently selected monovalent hydrocarbon groups free of aliphatic unsaturation or monovalent halogenated hydrocarbon groups free of aliphatic unsaturation, and each R 10 are independently selected from the group consisting of alkenyl and alkynyl, and the subscript aa is 0, 1, or 2, the subscript bb is 0 or more, the subscript cc is 1 or more, and the subscript dd is 0, 1, or 2, with the proviso that the quantity (aa+dd) is 2 or more and the quantity (aa+dd)=2, and with the proviso that the quantity (aa+bb+cc+dd) is 3 to 2,000. Alternatively, the subscript cc is 0 or more. Alternatively, the subscript bb is 2 or more. Alternatively, the quantity (aa+dd) is 2 to 10, alternatively 2 to 8, alternatively 2 to 6. Alternatively, the subscript cc is 0 to 1,000, alternatively 1 to 500, alternatively 1 to 200. Alternatively, the subscript bb is 2 to 500, alternatively 2 to 200, alternatively 2 to 100.

[0115] R 9 The monovalent hydrocarbon group is exemplified by an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a halogenated aralkyl group having 7 to 12 carbon atoms, where the alkyl, aryl, and halogenated alkyl are as described herein. Alternatively, each R 9 are independently monovalent hydrocarbon groups free of aliphatic unsaturation. Alternatively, each R 9 is an alkyl group. Alternatively, each R 9 are independently methyl, ethyl, or propyl. 9may be the same or different in each occurrence. Alternatively, each R 9 is a methyl group.

[0116] R 10 The monovalent hydrocarbon group having aliphatic unsaturation of R is capable of undergoing a hydrosilylation reaction. 10 Suitable aliphatic unsaturated hydrocarbon groups for are exemplified by alkenyl groups as defined herein and exemplified by vinyl, allyl, butenyl, and hexenyl, and alkynyl groups as defined herein and exemplified by ethynyl and propynyl. 10 may be vinyl or hexenyl. Alternatively, each R 10 is a vinyl group. The subscript in the unit formula (ii-I) above may be sufficient such that the alkenyl or alkynyl content of the branched siloxane of (ii-I) may be 0.1 wt % to 1 wt %, or alternatively 0.2 wt % to 0.5 wt %, based on the weight of the branched siloxane (ii-I).

[0117] (ii) When the polyorganosiloxane is substantially linear, or linear, the at least two aliphatic unsaturated groups can be attached to the silicon atom at pendant positions, terminal positions, or both pendant and terminal positions. Specific examples of polyorganosiloxanes having pendant silicon-bonded aliphatic unsaturated groups include starting material A) having the average unit formula: [(CH3)3SiO 1 / 2 ]2[(CH3)2SiO 2 / 2 ] cc [(CH3)ViSiO 2 / 2 ] bbwhere the subscripts bb and cc are as defined above, and Vi represents a vinyl group. With respect to this average formula, any methyl group may be replaced with a different monovalent hydrocarbon group (such as an alkyl or aryl), and any vinyl group may be replaced with a different aliphatically unsaturated monovalent hydrocarbon group (such as an allyl or hexenyl). Alternatively, as a specific example of a polyorganosiloxane having an average of at least two silicon-bonded aliphatically unsaturated groups per molecule, starting material (ii) may have the average formula Vi(CH3)2SiO[(CH3)2SiO] cc The silicon-bonded vinyl-terminated dimethylpolysiloxane may have the formula Si(CH3)2Vi, where the subscripts cc and Vi are defined above. The silicon-bonded vinyl-terminated dimethylpolysiloxane may be used alone or in combination with the dimethyl, methyl-vinylpolysiloxanes disclosed above. With respect to this average formula, any methyl group may be replaced with a different monovalent hydrocarbon group, and any vinyl group may be replaced with any terminal aliphatically unsaturated monovalent hydrocarbon group. Since the at least two silicon-bonded aliphatically unsaturated groups may be both pendant and terminal, (ii) the polyorganosiloxane may alternatively have the average unit formula [Vi(CH3)2SiO 1 / 2 ]2[(CH3)2SiO 2 / 2 ] cc [(CH3)ViSiO 2 / 2 ] bb where the subscripts bb and cc and Vi are defined above.

[0118] The substantially linear polyorganosiloxane may be a dimethylpolysiloxane capped at both molecular chain terminals with dimethylvinylsiloxy groups, a methylphenylpolysiloxane capped at both molecular chain terminals with dimethylvinylsiloxy groups, a methylphenylsiloxane-dimethylsiloxane copolymer capped at both molecular chain terminals with dimethylvinylsiloxy groups, a methylvinylsiloxane-methylphenylsiloxane copolymer capped at both molecular chain terminals with dimethylvinylsiloxy groups, or a methylvinylsiloxane-diphenylsiloxane copolymer capped at both molecular chain terminals with dimethylvinylsiloxy groups. Examples of such copolymers include methylvinylsiloxane-methylphenylsiloxane-dimethylsiloxane copolymers capped at both molecular chain terminals with dimethylvinylsiloxy groups, methylvinylsiloxane-methylphenylsiloxane copolymers capped at both molecular chain terminals with trimethylsiloxy groups, methylvinylsiloxane-diphenylsiloxane copolymers capped at both molecular chain terminals with trimethylsiloxy groups, and methylvinylsiloxane-methylphenylsiloxane-dimethylsiloxane copolymers capped at both molecular chain terminals with trimethylsiloxy groups.

[0119] Alternatively, starting material (ii) may comprise a substantially linear or linear polyorganosiloxane selected from the group consisting of: i) dimethylvinylsiloxy-terminated polydimethylsiloxane; ii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane); iii) dimethylvinylsiloxy-terminated polymethylvinylsiloxane; iv) trimethylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane); v) trimethylsiloxy-terminated polymethylvinylsiloxane; vi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), vii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane); viii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane); ix) phenyl, methyl, vinyl-siloxy terminated polydimethylsiloxane; x) dimethylhexenylsiloxy-terminated polydimethylsiloxane, xi) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane); xii) dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane; xiii) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane); xiv) Trimethylsiloxy-terminated polymethylhexenylsiloxane xv) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), xvi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane) and xvii) Combinations of these.

[0120] Alternatively, A) the polyorganosiloxane may be a resinous polyorganosiloxane having the average formula R 13 a” SiO (4-a”) / 2 [In the formula, each R 13 is as defined above, and the subscript a″ is selected such that 0.5≦a″≦1.7.

[0121] Resinous polyorganosiloxanes have a branched or three-dimensional network molecular structure. At 25°C, resinous polyorganosiloxanes may be in liquid or solid form. Alternatively, resinous polyorganosiloxanes can be exemplified by polyorganosiloxanes containing only T units, polyorganosiloxanes containing T units in combination with other siloxy units (e.g., M, D, and / or Q siloxy units), or polyorganosiloxanes containing Q units in combination with other siloxy units (i.e., M, D, and / or T siloxy units). Typically, resinous polyorganosiloxanes contain T units and / or Q units. Specific examples of resinous polyorganosiloxanes include vinyl-terminated silsesquioxanes and vinyl-terminated MDQ resins.

[0122] Alternatively, starting material (ii) may comprise (ii-I) a branched siloxane, (ii-II) a silsesquioxane, or both (ii-I) and (ii-II). Starting materials (ii-I) and (ii-II) may be particularly useful when the composition is used in release coating applications.

[0123] Starting material (ii) may be a combination of (ii-I) a branched siloxane and (ii-II) a silsesquioxane. This combination may be a physical blend or mixture. The branched siloxane and silsesquioxane are present in mutual amounts such that the amounts of (ii-I) the branched siloxane and (ii-II) the silsesquioxane add up to a total of 100 parts by weight, based on the total weight of all starting materials in the release coating composition. The branched siloxane may be present in an amount of 50 to 100 parts by weight, and the silsesquioxane may be present in an amount of 0 to 50 parts by weight. Alternatively, the branched siloxane may be present in an amount of 50 to 90 parts by weight, and the silsesquioxane may be present in an amount of 10 to 50 parts by weight. Alternatively, the branched siloxane may be present in an amount of 50 to 80 parts by weight, and the silsesquioxane may be present in an amount of 20 to 50 parts by weight. Alternatively, the branched siloxane may be present in an amount of 50 to 76 parts by weight, and the silsesquioxane may be present in an amount of 24 to 50 parts by weight. Alternatively, the branched siloxane may be present in an amount of 50 to 70 parts by weight, and the silsesquioxane may be present in an amount of 30 to 50 parts by weight. Without being bound by theory, it is believed that when the amount of silsesquioxane (ii-II) exceeds 50 parts by weight per 100 parts by weight of the combined amount of (ii-I) branched siloxane and (ii-II) silsesquioxane, release coatings formed from the compositions may suffer from migration, in which the silsesquioxane may migrate and become contaminated with an adherend, such as a pressure-sensitive adhesive, in contact with the release coating.

[0124] The starting material (ii-I) branched siloxane has the unit formula (ii-I), (R 9 3SiO 1 / 2 ) p (R 10 R 9 2SiO 1 / 2 ) q (R 9 2SiO 2 / 2 ) r (SiO 4 / 2 ) s [In the formula, each R 9are independently a monovalent hydrocarbon group free of aliphatic unsaturation or a monovalent halogenated hydrocarbon group free of aliphatic unsaturation, and each R 10 is an alkenyl or alkynyl group, both of which are as defined above, and may have the subscript p≧0, the subscript q>0, 15≧r≧995, and the subscript s>0.

[0125] In the unit formula (ii-I), the subscript p is ≧0. The subscript q is >0. Alternatively, the subscript q is ≧3. The subscript r is 15 to 995. The subscript s is >0. Alternatively, the subscript s is ≧1. Alternatively, for the subscript p, 22≧p≧0, or 20≧p≧0, or 15≧p≧0, or 10≧p≧0, or 5≧p≧0. Alternatively, for the subscript q, 22≧q≧0, or 22≧q≧4, or 20≧q>0, or 15≧q>1, or 10≧q≧2, or 15≧q≧4. Alternatively, for the subscript r, 800≧r≧15, or 400≧r≧15. Alternatively, for subscript s, 10≧s>0, alternatively, 10≧s≧1, alternatively, 5≧s>0, alternatively, s=1. Alternatively, subscript s is 1 or 2. Alternatively, when subscript s=1, subscript p may be 0 and subscript q may be 4.

[0126] The branched siloxane is represented by the formula (R 9 2SiO 2 / 2 ) m Alternatively, the branched siloxane may comprise at least two polydiorganosiloxane chains of the formula (R 9 2SiO 2 / 2 ) o wherein each subscript o is independently 1 to 100; 4 / 2 Alternatively, the branched siloxane may comprise at least one unit of the formula

[0127] [ka] wherein the subscript u is 0 or 1; each subscript t is independently 0 to 995, alternatively 15 to 995, alternatively 0 to 100; and each R 11 are independently selected monovalent hydrocarbon groups, as described above, and each R 9 are independently selected monovalent hydrocarbon radicals free of aliphatic unsaturation or monovalent halogenated hydrocarbon radicals free of aliphatic unsaturation, and each R 10 are each independently selected from the group consisting of alkenyl and alkynyl, as described above. Suitable branched siloxanes for starting material (ii-I) are exemplified by those disclosed in U.S. Pat. No. 6,806,339 and U.S. Patent Application Publication No. 2007 / 0289495.

[0128] Silsesquioxanes are represented by the unit formula (ii-II), (R 9 3SiO 1 / 2 ) i (R 10 R 9 2SiO 1 / 2 ) f (R 9 2SiO 2 / 2 ) g (R 9 SiO 3 / 2 ) h ([wherein, R 9 and R 10 is as above, with subscript i≧0, subscript f>0, subscript g is 15 to 995, and subscript h>0. Subscript i may be 0 to 10. Alternatively, for subscript i, 12≧i≧0, or 10≧i≧0, or 7≧i≧0, or 5≧i≧0, or 3≧i≧0.

[0129] Alternatively, the subscript f is ≧1. Alternatively, the subscript f is ≧3. Alternatively, for subscript f, 12≧f>0, or 12≧f≧3, or 10≧f>0, or 7≧f>1, or 5≧f≧2, or 7≧f≧3. Alternatively, for subscript g, 800≧g≧15, or 400≧g≧15. Alternatively, the subscript h is ≧1. Alternatively, the subscript h is 1 to 10. Alternatively, for subscript h, 10≧h>0, or 5≧h>0, or h=1. Alternatively, the subscript h is 1 to 10, or the subscript h is 1 or 2. Alternatively, if subscript h=1, the subscript f may be 3 and the subscript i may be 0. The value of subscript f may be sufficient to provide the silsesquioxane of unit formula (ii-II) with an alkenyl content of from 0.1 wt. % to 1 wt. %, alternatively from 0.2 wt. % to 0.6 wt. %, based on the weight of the silsesquioxane. Suitable silsesquioxanes for starting material (ii) are exemplified by those disclosed in U.S. Pat. No. 4,374,967.

[0130] Starting material (ii) may comprise a combination or two or more different polyorganosiloxanes that differ in at least one property, such as structure, molecular weight, monovalent groups bonded to silicon atoms, and content of aliphatic unsaturated groups, etc. The release coating composition may contain 60% to 98% by weight, alternatively 60% to 95% by weight, of starting material (ii) based on the total weight of all starting materials in the release coating composition.

[0131] Starting material (iii) hydrosilylation reaction catalyst The hydrosilylation catalyst used as starting material (iii) in the release coating composition can be as described and exemplified above for starting material (b). Alternatively, the hydrosilylation catalyst for use in the release coating composition can be selected from the group consisting of Karstedt's catalyst and Ashby's catalyst. (iii) The hydrosilylation catalyst is present in the release coating composition in a catalytic amount, i.e., an amount or quantity sufficient to promote its cure under the desired conditions. (iii) The catalytic amount of the hydrosilylation catalyst can be >0.01 ppm to 10,000 ppm, alternatively >1,000 ppm to 5,000 ppm. Alternatively, typical catalytic amounts of the (iii) hydrosilylation catalyst are 0.1 ppm to 5,000 ppm, alternatively 1 ppm to 2,000 ppm, alternatively >0 to 1,000 ppm. Alternatively, (iii) the catalytic amount of the hydrosilylation reaction catalyst can be from 0.01 ppm to 1,000 ppm, alternatively from 0.01 ppm to 100 ppm, alternatively from 20 ppm to 200 ppm, alternatively from 0.01 ppm to 50 ppm of platinum group metal, based on the combined weight of all starting materials in the release coating composition.

[0132] Starting material (iv) hydrosilylation reaction inhibitor Starting material (iv) is an inhibitor that can be used to alter the reaction rate of the release coating composition when compared to a composition containing the same starting material but without the added inhibitor. Inhibitors of the hydrosilylation curable compositions include acetylenic alcohols such as methylbutynol, ethynylcyclohexanol, dimethylhexynol, and 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, 4-ethyl-1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol, and combinations thereof; cycloalkenylsiloxanes such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl- ... methylvinylcyclosiloxanes exemplified by tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, as well as combinations thereof; ene-yne ​​compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne; triazoles such as benzotriazole; phosphines; mercaptans; hydrazine; amines such as tetramethylethylenediamine; dialkyl fumarates, dialkenyl fumarates, dialkoxyalkyl fumarates, maleates such as diallyl maleate; nitriles; ethers; carbon monoxide; alkenes such as cyclooctadiene, divinyltetramethyldisiloxane; alcohols such as benzyl alcohol; and combinations thereof. Alternatively, the hydrosilylation reaction inhibitor may be selected from the group consisting of acetylenic alcohols (e.g., 1-ethynyl-1-cyclohexanol), and maleates (e.g., diallyl maleate, diethyl maleate, or n-propyl maleate), and combinations of two or more thereof.

[0133] Alternatively, the starting material (iv) in the composition may be a silylated acetylenic compound. Without being bound by theory, it is believed that the addition of the silylated acetylenic compound reduces yellowing of the reaction product prepared from the hydrosilylation reaction of the composition when compared to the reaction product from the hydrosilylation of a composition that does not contain the silylated acetylenic compound or a composition that contains an organic acetylenic alcohol inhibitor such as those described above.

[0134] The silylated acetylene compounds are (3-methyl-1-butyn-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyn-3-oxy)dimethylsilane, bis(3-methyl-1-butyn-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyn-3-oxy))silane, (3-methyl-1-butyn-3-oxy)dimethylphenylsilane, (3-methyl-1-butyn-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyn-3-oxy)triethylsilane, bis(3-methyl-1- cyclohexyl-1-ethyn-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-oxy)trimethylsilane, (cyclohexyl-1-ethyn-1-oxy)trifluoropropylsilane, (3,5-dimethyl-1-hexyn-3-oxy)trimethylsilane, (3-phenyl-1-butyn-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyn-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyn-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyn-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-oxy)trimethylsilane, and combinations thereof. Alternatively, starting material (iv) is exemplified by methyl(tris(1,1-dimethyl-2-propynyloxy))silane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, or a combination thereof. Silylated acetylenic compounds useful as starting material (iv) can be prepared by methods known in the art, such as silylation of the above-mentioned acetylenic alcohols by reaction with chlorosilanes in the presence of an acid acceptor.

[0135] The amount of inhibitor added to the release coating composition will vary depending on a variety of factors, such as the desired pot life of the composition, whether the composition is a one-part or multi-part composition, the particular inhibitor used, the selection and amount of starting materials (i) and (ii), etc. However, if present, the amount of inhibitor may be from 0% to 1% by weight, alternatively from 0% to 5% by weight, alternatively from 0.001% to 1% by weight, alternatively from 0.01% to 0.5% by weight, or alternatively from 0.0025% to 0.025% by weight, based on the total weight of all starting materials in the composition.

[0136] Additional Starting Materials The release coating composition may optionally further comprise one or more additional starting materials selected from (v) anchor additives, (vi) anti-mist additives, (vii) release modifiers, (viii) substantially linear or linear polyorganohydrogensiloxanes, and (ix) solvents, such as those described above for starting material D).

[0137] (v) Anchor additives The starting material (v) is an anchor additive. Suitable anchor additives are exemplified by the reaction product of a vinylalkoxysilane with an epoxy-functional alkoxysilane; the reaction product of a vinylalkoxysilane with an epoxy-functional alkoxysilane; and a combination (e.g., a physical blend and / or reaction product) of a polyorganosiloxane having at least one aliphatic unsaturated hydrocarbon group and at least one hydrolyzable group per molecule with an epoxy-functional alkoxysilane (e.g., a combination of a hydroxy-terminated vinyl-functional polydimethylsiloxane with glycidoxypropyltrimethoxysilane). Alternatively, the anchor additive may comprise a polyorganosilicate resin. Suitable anchor additives and their preparation methods are disclosed, for example, in U.S. Pat. No. 9,562,149, U.S. Patent Application Publication Nos. 2003 / 0088042, 2004 / 0254274, and 2005 / 0038188, and European Patent No. 0556023. Although the exact amount of anchor additive will vary depending on various factors, such as the type of substrate and whether a primer is used, the amount of anchor additive in the release coating composition may be from 0 to 2 parts by weight per 100 parts by weight of starting material (ii). Alternatively, the amount of anchor additive may be from 0.01 to 2 parts by weight per 100 parts by weight of starting material (ii).

[0138] (vi) Anti-mist additives The starting material (vi) is a mist suppressing additive that can be added to the release coating composition to reduce or suppress the formation of silicone mist during the coating process, especially in high-speed coating equipment.The mist suppressing additive can be a reaction product of an organohydrogensilicon compound, an oxyalkylene compound, or an organoalkenylsiloxane having at least three silicon-bonded alkenyl groups per molecule, and a suitable catalyst.Suitable anti-fog agents are disclosed, for example, in U.S. Patent Application Publication No. 2011 / 0287267, U.S. Patent No. 8,722,153, U.S. Patent No. 6,586,535, and U.S. Patent No. 5,625,023.

[0139] The amount of anti-mist additive will vary depending on various factors, such as the amount and type of other starting materials selected for the release coating composition, but the amount of anti-mist additive may be from 0% to 10% by weight, or alternatively from 0.1% to 3% by weight, based on the total weight of all starting materials in the release coating composition.

[0140] (vii) release modifiers Starting material (vii) is a release modifier that can be added to a release coating composition to control (reduce) the level of release force (i.e., the adhesive strength between the release coating and the substrate, such as a label, including a pressure-sensitive adhesive). A release coating composition with the required release force can be formulated from a modifier-free release coating composition by adjusting the modifier concentration. Examples of suitable release modifiers include trimethylsiloxy-terminated dimethyl, phenylmethylsiloxane copolymers. Alternatively, the release modifier may be a condensation reaction product of an organopolysiloxane resin having hydroxyl or alkoxy groups and a diorganopolysiloxane having at least one hydroxyl or hydrolyzable group. When used, the release modifier can be used in an amount of, for example, 0 to 85 parts by weight, or 25 to 85 parts by weight, per 100 parts of starting material (ii). Examples of suitable release modifiers are disclosed, for example, in U.S. Pat. No. 8,933,177 and U.S. Patent Application Publication No. 2016 / 0053056.

[0141] (viii) Linear polyorganohydrogensiloxane Starting material (viii) is a substantially linear or linear polyorganohydrogensiloxane different from starting material (i) that can be added as an additional crosslinker to the release coating composition. The substantially linear or linear polyorganohydrogensiloxane has the unit formula (HR 12 2SiO 1 / 2 ) v’ (HR 12 SiO 2 / 2 ) w’ (R 12 2SiO2 / 2 ) x’ (R 12 3SiO 1 / 2 ) y’ [In the formula, each R 12 are independently selected monovalent hydrocarbon radicals, the subscript v' is 0, 1, or 2, the subscript w' is 1 or more, the subscript x' is 0 or more, and the subscript y' is 0, 1, or 2, with the proviso that the quantity (v'+y')=2 and the quantity (v'+w')≧3. 12 The monovalent hydrocarbon group of R 1 The monovalent hydrocarbon group may be as described above. The number (v'+w'+x'+y') may be 2 to 1,000. The polyorganohydrogensiloxane may be i) dimethylhydrogensiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymer; ii) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane; iii) trimethylsiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymers, and iv) trimethylsiloxy-terminated polymethylhydrogensiloxane, and v) is exemplified by a combination of two or more of i), ii), iii), iv), and v). Suitable polyorganohydrogensiloxanes are commercially available from Dow Silicones Corporation (Midland, Michigan, USA).

[0142] (ix) solvent Starting material (x) is a solvent. Suitable solvents include the hydrocarbons described above as starting material D) in the method for producing polyfunctional organohydrogensiloxanes. Alternatively, the solvent may be selected from polyalkylsiloxanes, alcohols, ketones, glycol ethers, tetrahydrofuran, mineral spirits, naphtha, tetrahydrofuran, mineral spirits, or combinations thereof. Polyalkylsiloxanes with suitable vapor pressures can be used as solvents, including hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyalkylsiloxanes, such as 0.5-1.5 cSt DOWSIL™ 200 Fluids and DOWSIL™ OS Fluids, commercially available from Dow Silicones Corporation (Midland, Michigan, USA).

[0143] Alternatively, starting material (x) may comprise an organic solvent, which may be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; a ketone such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether, or tetrahydrofuran; mineral spirits; naphtha; or a combination thereof.

[0144] The amount of solvent will vary depending on various factors, such as the type of solvent selected and the amount and type of other starting materials selected for the release coating composition. However, the amount of solvent can be from 0% to 99%, or alternatively, from 2% to 50%, based on the weight of all starting materials in the release coating composition. The solvent can be added during preparation of the release coating composition, for example, to aid in mixing and delivery. All or a portion of the solvent can optionally be removed after preparation of the release coating composition.

[0145] Other optional starting materials that may be further added to the release coating compositions described herein include, for example, reactive diluents, fragrances, preservative colorants, and fillers such as silica, quartz, or chalk.

[0146] In selecting starting materials for the release coating composition (and other curable compositions described herein), certain starting materials described herein may have more than one function, and therefore the types of starting materials may overlap. For example, certain particulates, such as carbon black, may be useful as fillers, colorants, such as pigments, and even flame retardants. If additional starting materials are added to the release coating composition, the additional starting materials are different from starting materials (i)-(iv) and different from each other.

[0147] Alternatively, the release coating may be free of particulates or may contain only limited amounts of particulates (e.g., fillers and / or pigments), e.g., 0% to 30% by weight of the release coating composition. Particulates may agglomerate or otherwise adhere to the coater equipment used to apply the release coating. They may interfere with the optical properties, e.g., transparency, of the release coating and release liner formed therefrom, if optical clarity is desired. Particulates may be detrimental to adherend adhesion.

[0148] Alternatively, the release coating composition of the present invention may be free of fluoroorganosilicone compounds. Due to their low surface tension during curing, fluorocompounds are believed to rapidly migrate to the interface between the coating composition and the substrate, e.g., the polyorganosiloxane release coating composition / PET film interface, forming a fluorine-containing barrier that interferes with the adhesion of the release coating (prepared by curing the release coating composition) to the substrate. By creating a barrier, the fluorocompound may prevent any starting materials from reacting at the interface. Furthermore, fluorosilicone compounds are typically expensive.

[0149] The stripping composition can be prepared by combining starting materials including (i), (ii), (iii), and (iv) above, along with any optional additional starting materials, in any order of addition, optionally via masterbatch, and optionally under shear.

[0150] Method for coating substrates A method for preparing a substrate coated with a curable composition includes disposing the curable composition on a substrate. The method further includes curing the curable composition on the substrate. Curing can be carried out by heating at an elevated temperature, for example, from 50°C to 180°C, alternatively from 50°C to 120°C, alternatively from 50°C to 90°C, to obtain a coated substrate. One skilled in the art will be able to select an appropriate temperature depending on various factors, including the selection of optional starting materials in the curable composition and the substrate material of construction.

[0151] The curable composition can be disposed or dispensed onto a substrate in any suitable manner. Typically, the curable composition is applied in wet form by a wet coating technique. The curable composition can be applied by i) spin coating, ii) brush coating, iii) drop coating, iv) spray coating, v) dip coating, vi) roll coating, vii) flow coating, viii) slot coating, ix) gravure coating, x) Mayer bar coating, or xi) a combination of any two or more of i)-x). Typically, disposing the curable composition on a substrate results in a wet deposit on the substrate, which is then cured to obtain a coated substrate comprising a cured film formed from the curable composition on the substrate.

[0152] The substrate is not limited and may be any substrate. The cured film may be separable from the substrate or may be physically and / or chemically bonded to the substrate, depending on the choice. The substrate may be subjected to an integrated hotplate or an integrated or stand-alone oven to cure the deposit. The substrate may optionally have continuous or discontinuous shapes, sizes, dimensions, surface roughness, and other properties. Alternatively, the substrate may have an elevated softening point temperature. However, the curable compositions and methods are not so limited.

[0153] Alternatively, the substrate may comprise a plastic, which may be thermoset and / or thermoplastic, but alternatively, the substrate may be glass, metal, paper, wood, cardboard, paperboard, silicone, or a polymeric material, or a combination thereof.

[0154] Specific examples of suitable substrates include paper substrates such as kraft paper, polyethylene-coated kraft paper (PEK-coated paper), and plain paper; polymer substrates such as polyamide (PA); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyester; polyolefins such as polyethylene (PE), polypropylene (PP), and polybutylene; styrene resins; polyoxymethylene (POM); polycarbonate (PC); polymethylene methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); and polyphenylene ether (polyphenylene ether (PPE); polyimide (PI); polyamideimide (PAI); polyetherimide (PEI); polysulfone (PSU); polyethersulfone; polyketone (PK); polyetherketone; polyvinyl alcohol (PVA); polyetheretherketone (PEEK); polyetherketoneketone (PEKK); polyarylate (PAR); polyethernitrile (PEN); phenolic resin; phenoxy resin; cellulose such as triacetyl cellulose, diacetyl cellulose, and cellophane; fluorinated resins such as polytetrafluoroethylene;Thermoplastic elastomers such as polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, and fluoro-type elastomers; and copolymers and combinations thereof.

[0155] The curable composition, or wet deposit, is typically cured at elevated temperature for a period of time. The period of time is typically sufficient to effect cure, i.e., crosslinking, of the curable composition. The period of time may be from greater than 0 to 8 hours, alternatively from greater than 0 to 2 hours, alternatively from greater than 0 to 1 hour, alternatively from greater than 0 to 30 minutes, alternatively from greater than 0 to 15 minutes, alternatively from greater than 0 to 10 minutes, alternatively from greater than 0 to 5 minutes, or alternatively from greater than 0 to 2 minutes. The period of time will vary depending on various factors, such as the elevated temperature used, the temperature selected, the desired film thickness, and the absence of any water or carrier vehicle in the curable composition.

[0156] Curing the curable composition typically has a residence time of 0.1 seconds to 50 seconds, alternatively 1 second to 10 seconds, alternatively 0.5 seconds to 30 seconds. The residence time selected can vary depending on the substrate selection, the selected temperature, and the line speed. As used herein, residence time refers to the time the curable composition or wet deposit is exposed to an elevated temperature. Residence time is distinct from cure time because there may be ongoing curing even after the curable composition, wet deposit, or partially cured reaction intermediate thereof is no longer exposed to the elevated temperature that typically initiates curing. Alternatively, the coated article can be prepared on a conveyor belt in an oven, and residence time can be calculated by dividing the length of the oven (e.g., in meters) by the line speed of the conveyor belt (e.g., meters / second).

[0157] The time can be subdivided into cure iterations, e.g., a first cure and a post cure, e.g., 1 hour for the first cure and 3 hours for the post cure. The elevated temperature can be independently selected in such iterations from any temperature above room temperature and can be the same in each iteration.

[0158] Depending on the thickness and other dimensions of the film and coated substrate, the coated substrate can be formed through an iterative process. For example, a first deposit can be formed and exposed to a first elevated temperature for a first period of time to obtain a partially cured deposit. A second deposit can then be placed on the partially cured deposit and exposed to a second elevated temperature for a second period of time to obtain a second partially cured deposit. This partially cured deposit can also be further cured while exposed to the second elevated temperature for a second period of time. A third deposit can be placed on the second partially cured deposit and exposed to a third elevated temperature for a third period of time to obtain a third partially cured deposit. The second partially cured deposit can also be further cured while exposed to the second elevated temperature for a second period of time. This process can be repeated, for example, 1 to 50 times, to obtain the desired structure of the coated article. The composite of partially cured layers can then be subjected to a final post-cure, for example, at the elevated temperature and time described above. Each elevated temperature and time can be independently selected and can be the same or different from each other. When the article is formed via an iterative process, each deposit may also be independently selected and may differ in the starting materials selected in the curable composition, their amounts, or both, or, alternatively, each repeating layer may be fully cured rather than only partially cured in such an iterative process.

[0159] Alternatively, the deposition may comprise a wet film. Alternatively, the iterative process may be wet-on-wet, depending on the state of cure of the partially cured layer. Alternatively, the iterative process may be wet-on-dry.

[0160] Coated substrates comprising a film formed from a curable composition on a substrate can have a variety of dimensions, including the relative thicknesses of the film and the substrate. The film has a thickness that can vary depending on the end use. The film may have a thickness of greater than 0 to 4,000 μm, alternatively greater than 0 to 3,000 μm, alternatively greater than 0 to 2,000 μm, alternatively greater than 0 to 1,000 μm, alternatively greater than 0 to 500 μm, or alternatively greater than 0 to 250 μm. However, other thicknesses, e.g., 0.1 to 200 μm, are also contemplated. For example, the film thickness may be 0.2 to 175 μm, alternatively 0.5 to 150 μm, alternatively 0.75 to 100 μm, alternatively 1 to 75 μm, alternatively 2 to 60 μm, alternatively 3 to 50 μm, or alternatively 4 to 40 μm. Alternatively, when the substrate is plastic, the film may have a thickness of from greater than 0 to 200 μm, alternatively from greater than 0 to 150 μm, alternatively from greater than 0 to 100 μm.

[0161] If desired, the film can undergo further processing depending on its end use. For example, the film can undergo oxide deposition (e.g., SiO deposition), resist deposition and patterning, etching, chemical stripping, corona or plasma stripping, metallization, or metal deposition. Such further processing techniques are generally known. Such deposition can be chemical vapor deposition (such as low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and plasma-assisted chemical vapor deposition), physical vapor deposition, or other vacuum deposition techniques. Many such further processing techniques involve high temperatures, particularly vacuum deposition, for which the film is well suited given its excellent thermal stability. However, depending on the end use of the film, the film can be utilized after such further processing.

[0162] The coated substrates can be utilized in a variety of end uses. For example, the coated substrates can be utilized in coating applications, packaging applications, adhesive applications, fiber applications, fabric or textile applications, construction applications, transportation applications, electronics applications, or electrical applications. However, the curable compositions can be utilized for end uses other than preparing coated substrates, such as preparing articles such as silicone rubber.

[0163] Alternatively, the coated substrate can be utilized as a release liner for a tape or adhesive, including any pressure-sensitive adhesive, such as, for example, acrylic resin-type pressure-sensitive adhesives, rubber-type pressure-sensitive adhesives, and silicone-type pressure-sensitive adhesives, as well as acrylic resin-type adhesives, synthetic rubber-type adhesives, silicone-type adhesives, epoxy resin-type adhesives, and polyurethane-type adhesives. Each major surface of the substrate can have a film disposed thereon for a double-sided tape or adhesive.

[0164] Alternatively, when the curable composition is formulated as a release coating composition, the release coating composition can be prepared by mixing the starting materials together, e.g., to prepare a one-part composition. However, it may be desirable to prepare the release coating composition as a multi-part composition in which the starting material having SiH functionality (e.g., starting material (i)), the hydrosilylation reaction catalyst, and the like are stored in separate parts until the parts are combined at the time of use (e.g., immediately prior to application to a substrate).

[0165] For example, a multi-part composition may include: Part (A) is a base part comprising: (ii) a polyorganosiloxane having an average of at least two silicon-bonded aliphatically unsaturated hydrocarbon groups per molecule; (iii) a hydrosilylation reaction catalyst; and, if present, one or more of an anchor additive and a solvent; The release coating composition may also include a (B) curing agent part, which includes (ii) a polyorganosiloxane having an average of at least two silicon-bonded aliphatically unsaturated hydrocarbon groups per molecule, (i) a polyfunctional organohydrogensiloxane, and, if present, (viii) a substantially linear or linear polyorganohydrogensiloxane, an anchor additive, and a solvent. The starting material (iv) inhibitor can be added to either part (A), part (B), or both. Parts (A) and (B) may be combined in an (A):(B) weight ratio of 1:1 to 10:1, alternatively 1:1 to 5:1, alternatively 1:1 to 2:1. Parts (A) and (B) can be provided in a kit, along with instructions, for example, on how to combine the parts to prepare the release coating composition, how to apply the release coating composition to a substrate, and how to cure the release coating composition.

[0166] Alternatively, if an anchor additive is present, it can be incorporated into either part (A) or part (B), or can be added to a separate (third) part.

[0167] Alternatively, the release coating composition comprises: 1) ii) mixing starting materials including a polyorganosiloxane having an average of at least two silicon-bonded aliphatically unsaturated hydrocarbon groups per molecule, (i) a polyfunctional organohydrogensiloxane, (iii) a hydrosilylation reaction catalyst, (iv) an inhibitor, and optionally one or more of (v) an anchoring additive, (vi) a mist suppressing additive, (vii) a release control agent, (viii) a linear polyorganohydrogensiloxane, and (ix) a solvent, thereby forming a release coating composition; 2) applying the mixture onto a substrate. Step 1) can be performed by mixing parts (A) and (B) of the multi-part composition, as described above.

[0168] The release coating composition can be applied to the substrate by any convenient means such as spraying, doctor blading, dipping, screen printing, or by a roll coater, for example, an offset web coater, kiss coater, or etched cylinder coater.

[0169] The release coating composition of the present invention can be applied to any substrate, such as those described above. Alternatively, the release coating composition can be applied to a polymeric film substrate, such as a polyester film, particularly a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, or a polystyrene film. Alternatively, the release coating composition can be applied to a paper substrate, including a plastic-coated paper, such as polyethylene-coated paper, glassine, supercalendered paper, or clay-coated kraft paper. Alternatively, the release coating composition can be applied to a metal foil substrate, such as aluminum foil.

[0170] The method may further include the step of 3) treating the substrate and then coating the substrate with a release coating composition. The treatment of the substrate can be carried out by any convenient means, such as plasma treatment or corona discharge treatment. Alternatively, the substrate can be treated by applying a primer. In certain cases, if the substrate is treated before coating, the adhesion of the release coating can be improved.

[0171] If the release coating composition includes a solvent, the method may further include the step of 4) removing the solvent, which may be carried out by any conventional means, such as by heating at 50°C to 100°C for a time sufficient to remove all or a portion of the solvent. The method may further include the step of 5) curing the release coating composition to form a release coating on the surface of the substrate. Curing may be carried out by any conventional means, such as by heating at 100°C to 200°C.

[0172] Under production coater conditions, curing can be carried out at air temperatures of 120°C to 150°C with dwell times of 1 to 6 seconds, or alternatively 1.5 to 3 seconds. Heating for steps 4) and / or 5) can be carried out in an oven, such as an air circulating oven or tunnel furnace, or by passing the coated film around a heated cylinder. [Example]

[0173] These examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention as set forth in the claims. The starting materials listed in Table 1 and Reference Examples 1 and 2 were used in the examples herein.

[0174] [Table 1]

[0175] Reference Example 1 - General Procedure Unless otherwise noted, all experimental procedures and manipulations of chemicals were performed in a nitrogen-purged glovebox or on a Schlenk line. All bulk reaction solvents (toluene, diethyl ether, hexane, tetrahydrofuran (THF)) were dried by passage through columns of alumina and Q5 reactive scavenger. All other solvents were purchased anhydrous grade from Aldrich and stored over activated 3 Å molecular sieves before use. NMR solvents (CDCl3, CD2Cl2, and CD6D6) obtained from Cambridge Isotope Laboratories, Inc. were dried over activated 3 Å molecular sieves or, in the case of CD6D6, dried using Na / K alloy. 1-Bromo-3,5-bis(trifluoromethyl)benzene, 1-bromo-2,5-bis(trifluoromethyl)benzene, 1-bromo-2,6-difluorobenzene, 1-bromo-2,4,6-trifluorobenzene, and 1-bromo-4-trifluoromethylbenzene were purchased from Oakwood Chemical. 1-Bromo-2,3,5,6-tetrafluoro-4-trifluoromethylbenzene was purchased from Alfa Aesar. FAB was purchased from TCI. All other reagents were purchased from Sigma-Aldrich and used as received. n-Butyllithium (solution in hexane) was titrated before use using 1.00 M decanol in toluene with 1,10-phenanthroline as the indicator. 1 Watson, SC; Eastham, JF "Colored indicators for simple direct titration of magnesium and lithium reagents", J. Organomet. Chem., 1967, 9, 165-168.

[0176] Multinuclear NMR spectrum ( 1 H, 13 C. 19 F, 29 Si, 11 B) were collected on one of the following instruments: a Varian MR-400 or a Varian VNMRS-500. 11B NMR spectra were collected exclusively on a Varian VNMRS-500. 1 H and 13 C NMR chemical shifts were referenced in parts per million to the residual solvent peak. 1 5.32 ppm for H-CD2Cl2, 7.15 ppm for C6D6, and 7.25 ppm for CDCl3. 13 54.00 ppm for C-CD2Cl2, 128.00 ppm for C6D6, and 77.00 ppm for CDCl3. 11 B NMR chemical shifts are externally referenced to BF3(Et2O) (0 ppm) 19 F NMR chemical shifts were externally referenced to CFCl (0 ppm). Subambient reaction temperatures were measured using an Extech Instruments EasyView™ 10 Dual K model EA 10 thermometer equipped with a fine JKEM sensor PTFE wire K 36INJ, except when dry ice or ice was the only cooling means.

[0177] Reference Example 2 - Synthesis Procedure - Preparation of Starting Materials Lithium (diethyl etherate) (3,5-bis(trifluoromethyl)phenyl) triisopropoxyborate was prepared as follows.

[0178] [ka]

[0179] To a cooled (-78 °C, CO2(s) bath) solution of 1-bromo-3,5-bis(trifluoromethyl)benzene (18.52 g, 63.19 mmol) in diethyl ether (200 mL) was added n-butyllithium (23.0 mL, 2.61 M in hexanes, 60.03 mmol) with stirring. The reaction mixture was stirred at -78 °C for 3 hours, forming a precipitate. Triisopropyl borate (11.86 g, 63.06 mmol) in ether (20 mL) was slowly added. The reaction mixture was stirred at -78 °C for 1 hour, then warmed to ambient temperature and stirred for 1 hour to give a slightly cloudy solution. The reaction mixture was filtered, and the volatiles were removed under reduced pressure to give a solid. The resulting solid was triturated with hexane, filtered, and the volatiles were removed under reduced pressure to give the product as a colorless powder. Yield: 23.16 g, 94.53%. The compound was first isolated as its ether adduct.

[0180] 1 H NMR(500MHz,THF-d8)δ8.15(s,2H),7.57(s,1H),3.79(p,J=6.1Hz,3H),0.95(d,J=6.1Hz,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 (470 MHz, THF-d8) δ -63.02. 11 B NMR (160 MHz, THF-d8) δ 3.84.

[0181] (3,5-bis(trifluoromethyl)phenyl)diisopropoxyborane was prepared as follows.

[0182] [ka]

[0183] To a solution of lithium (diethyl etherate)(3,5-bis(trifluoromethyl)phenyl)triisopropoxyborate (8.00 g, 19.6 mmol) in diethyl ether (100 mL) was added hydrogen chloride solution (12.3 mL, 2 M in ether, 24.6 mmol), and a precipitate formed immediately. The reaction mixture was stirred for 2 hours, filtered, and the volatiles were removed under reduced pressure. The resulting residue was extracted with hexane, filtered, and the volatiles were removed under reduced pressure to give the product as an oil. Yield: 5.10 g, 76.1%.

[0184] 1 H NMR (500MHz, chloroform-d) δ8.01(d,J=1.9Hz,2H),7.89(dt,J=2.0,1.0Hz,1H),4.59(hept,J=6.1Hz,1H),1.27(d,J=6.2Hz,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.

[0185] Lithium (diethyl etherate) bis(3,5-bis(trifluoromethyl)phenyl) diisopropoxyborate was prepared as follows.

[0186] [ka]

[0187] To a cooled (-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-butyllithium (5.30 mL, 2.61 M in hexane, 60.0 mmol) with stirring. The reaction mixture was stirred at -78°C for 1 hour, and a precipitate formed. (3,5-bis(trifluoromethyl)phenyl)diisoproxiborane (4.82 g, 14.1 mmol) in ether (15 mL) was slowly added. The reaction mixture was stirred at -78°C for 1 hour (some solids visible), then warmed to ambient temperature and stirred overnight to give a clear solution. Volatiles were removed under reduced pressure to give a crystalline-appearing 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 formed. The supernatant was decanted and the volatiles removed under reduced pressure to give a colorless crystalline material. Yield: 8.23 ​​g, 93.5%.

[0188] 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.

[0189] Bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane was prepared as follows.

[0190] [ka]

[0191] To a solution of lithium (diethyl etherato)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, 2 M in ether, 11 mmol), and a precipitate formed immediately. The reaction mixture was stirred for 1 h and the volatiles were removed under reduced pressure. The residue was extracted with hexane, filtered, and the volatiles were removed under reduced pressure to give the product as a colorless powder. Yield: 3.98 g, 102% (some residual solvent present).

[0192] 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.

[0193] Synthesis procedure - catalyst preparation Catalyst sample C1, tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct, was prepared as follows.

[0194] Preparation of lithium isopropoxytris(3,5-bis(trifluoromethyl)phenyl)borate

[0195] [ka]

[0196] To a cooled (-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), n-butyllithium (5.00 mL, 2.5 M in hexane, 12.7 mmol) was slowly added dropwise. The reaction mixture was stirred at -78 °C for 1 hour. Isopropoxybis(3,5-bis(trifluoromethyl)phenyl)borane (6.29 g, 12.7 mmol) in 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 ether, and the solution was placed in a freezer. After cooling overnight, the supernatant was decanted from the formed crystals, and the crystals were dried under reduced pressure to give 6.74 g. The supernatant solution was concentrated and chilled in the freezer overnight to give a second crop of crystalline material (1.54 g). Total yield: 8.28 g, 75.6%.

[0197] 1 H NMR (400MHz, benzene-d6) δ8.09(s,6H),7.74(s,3H),3.71(p,J=6.1Hz,1H),2.97(q,J=7.0Hz,10H),0.70(t,J=7.1Hz,15H),0.67(d,J=6.2Hz,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.

[0198] Preparation of tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct

[0199] [ka]

[0200] To a solution of lithium isopropoxytris(3,5-bis(trifluoromethyl)phenyl)borate (6.700 g, 7.75 mmol) in ether (100 mL) was added chlorotrimethylsilane (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 removed under reduced pressure to give the product as a colorless solid, 4.80 g, 95.2%.

[0201] A portion of the solid (4.041 g) was dissolved in ether (100 mL) and THF (5 mL) was added. Volatiles were removed from the reaction mixture under reduced pressure. The residue was extracted with benzene, filtered, and 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%.

[0202] 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.

[0203] Catalyst sample C2, bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct, was prepared as follows.

[0204] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane

[0205] [ka]

[0206] To a cooled (-78 °C, CO2(s) / acetone bath) solution of 1-bromo-4-trifluoromethylbenzene (2.750 g, 12.22 mmol) in diethyl ether (200 mL) was slowly added dropwise n-butyllithium (4.70 mL, 2.535 M in hexanes, 11.9 mmol). 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 allowed to warm to ambient temperature with stirring overnight to give a clear yellow solution with a trace of precipitate. The solvent was removed under reduced pressure to give a thick yellow oil. The oil was rapidly stirred with hexane (100 mL) overnight (some cloudiness occurred). The hexane layer was decanted, filtered, and the volatiles were removed under reduced pressure. The oil layer was extracted again with hexane, and the process was repeated several times. A small amount of oil that did not dissolve was discarded. The volatiles were removed from the filtrate under reduced pressure to give a yellow oil. The oil was dissolved in diethyl ether (100 mL), and trimethylsilyl chloride (TMSCl, 1.5 g, 13.8 mmol) was added. A large amount of precipitate formed within 30 minutes. The reaction mixture was stirred overnight. The reaction mixture was filtered, and the volatiles were removed under reduced pressure to give a pasty beige sludge. The NMR spectrum indicated a nearly complete reaction. The product was dissolved in ether, and additional TMSCl was added (0.4 mL). After stirring for several hours, the volatiles were removed under reduced pressure. The residue was extracted with benzene, filtered, and the volatiles were removed under reduced pressure to give a pasty solid. 1 H NMR spectroscopy still showed 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 give the product as a white solid (5.370 g, 68.90%).

[0207] 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). 13 C NMR (126 MHz, benzene-d6) δ 149.08, 148.88, 134.18, 133.62 (d, J = 3.8 Hz), 131.11 (q, J = 32.4 Hz), 129.94 (q, J = 32.1 Hz), 125.06 (d, J = 272.1 Hz), 124.92 (q, J = 3.8 Hz), 124.34 (q, J = 272.7 Hz), 121.22 (dt, J = 8.0, 4.0 Hz), 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.

[0208] Catalyst sample C3, bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct, was prepared as follows.

[0209] Preparation of lithium bis(diethyl etherate)bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)-isopropoxyborate

[0210] [ka]

[0211] In an N2-purged glovebox, 2.06 g (9.78 mmol) of 1-bromo-2,4,6-trifluorobenzene was mixed with 80 mL of diethyl ether in a 250 mL Schlenk flask. A Teflon-coated stir bar was added to the colorless solution, and the flask was sealed with a rubber septum before removing it from the glovebox. In a fume hood, the flask was connected to a nitrogen line and placed in a dry ice / acetone bath (-78 °C) for 20 minutes to cool. A 2.5 M solution of n-butyllithium in hexane (4.3 mL, 10.8 mmol) was added to the cooled solution via syringe. The reaction mixture was stirred at -78 °C for 1 hour. A solution of 4.85 g of bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane in 20 mL of diethyl ether was prepared in the glovebox and drawn up into a syringe. The solution was poured into a flask containing the cold aryllithium solution at -78 °C, and the mixture was stirred at this temperature for 30 min. The dry ice / acetone bath was removed, and the reaction mixture was allowed to slowly warm to room temperature with stirring overnight. The next morning, all volatiles were removed under vacuum to yield a sticky yellow solid. The flask was returned to the glovebox, and the sticky yellow material was extracted with 1) 80 mL of pentane, 2) 80 mL of hexane, and 3) 60 mL of a 50 / 50 ether / hexane mixture. All three solutions were placed in the glovebox freezer overnight (-40 °C), causing a white crystalline material to precipitate from solution. The crystalline material was collected by filtration, washed with cold pentane (-40 °C), and dried under vacuum for 1 h. Total yield: 5.29 g (impure, approximately 5.5 mmol of the desired lithium salt, 56%). Note that pure material was not obtained. The lithium salt was contaminated with the isopropoxyborane starting material (12%–22% contamination, depending on the batch of solid material recovered). It was decided to carry the isolated material forward to the next step in the reaction without further purification.

[0212] 1H NMR(400MHz,benzene-d6)δ8.26(s,4H,ortho-ArCH),7.80(s,2H,para-ArCH),6.22-6.07(m,2H,ortho-ArCH),3.68(hept, J=5.8Hz,1H,CH(CH3)2),3.07(q,J=7.1Hz,8H,OCH2),0.81(t,J=7.1Hz,12H,OCH2CH3),0.67(d,J=6.2Hz,6H,CH(CH3)2). 13 C 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,ortho-ArCH),130.7(q,J=31.9Hz,ArC-CF3),125.5(q,J=272.4Hz,CF3),119.9(p,J=4.0Hz,para-ArCH),10 1.0(ddd,J=36.6,24.0,3.7Hz,meta-ArCH),65.9(s,OCH(CH3)2),65.8(s,OCH2CH3),25.7(s,OCH(CH3)2),14.7(s,OCH2CH3). 19 F NMR (376MHz, benzene-d6)δ-62.7(s,12F,CF3),-104.4(brs,2F,ortho-ArF),-112.3(m,1F,para-ArF).

[0213] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoroborane)

[0214] [ka]

[0215] In an N2-purged glovebox, 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: The lithium borate salt was contaminated with 22% bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane). Chlorotrimethylsilane (1.0 mL, 7.9 mmol) was added to the room temperature solution with stirring. There was no immediate sign of reaction. The mixture was stirred overnight at room temperature. The next morning, a large amount of LiCl precipitate had formed in the flask. An aliquot of the reaction mixture was removed and 19 Analysis by F NMR spectroscopy confirmed the reaction was complete. The reaction mixture was filtered through Celite to remove LiCl, and the filtrate was pumped to dryness. The resulting sticky white solid was extracted with 80–90 mL of hexane and filtered again. The hexane solution was placed in a glovebox freezer overnight (−40 °C), during which time a white microcrystalline solid precipitated. The solid was collected by filtration, washed with 5–10 mL of cold pentane (−40 °C), and dried under vacuum for 1 h. Multinuclear NMR spectroscopy confirmed the formation of the desired material in pure form. Yield: 0.992 g, 1.75 mmol, 53.2%.

[0216] 1 H NMR (400 MHz, benzene-d6) δ 7.88 (s, 6H, ArCH on CF3-substituted ring), 6.03 (m, 2H, ArCH on 2,4,6-trifluorophenyl ring). 13 C NMR(101MHz,benzene-d6)δ167.4(dt,J=257.6,16.2Hz,para-ArCF),166.2(dt,J=253.5,15.2Hz,ortho-ArCF),142.8(br s,ArC),137.5(d,J=3.0Hz,ortho-ArCH),132.1(q,J=33.4Hz,ArC-CF3),126.9(pent,J=4.0Hz,para-ArCH),124.1(q,J=273.0Hz,CF3),112.6(br s,ArC),101.6(ddd,J=29.0,24.9,3.7Hz,meta-ArCH). 19F NMR(376MHz,benzene-d6)δ-63.1(s,12F,CF3),-92.4(m,2F,ortho-ArCF),-98.5(s,1F,para-ArCF). 11 B NMR (160 MHz, benzene-d6) δ 62.9 (broad s).

[0217] Preparation of the THF adduct of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoroborane)

[0218] [ka]

[0219] In an N2-purged glovebox, 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 vial and dissolved in 50 mL of THF. The THF was removed under vacuum with stirring to give a white solid. The solid was triturated with 40 mL of pentane to aid in the removal of 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-trifluorophenyl)borane. Yield: 0.969 g, 1.51 mmol, 86.3%.

[0220] 1 H NMR (400MHz, benzene-d6) δ7.96(s,4H,ortho-ArCH),7.79(s,2H,para-ArCH),6.16(t,J=8.0Hz,2H,meta-ArCH),3.10(m,4H,OCH2),0.79(m,4H,CH2). 13C NMR(101MHz, benzene-d6)δ165.3(ddd,J=245.4,17.7,14.3Hz,ortho-ArCF),163.9(dd,J=249.5,16.2Hz,para-ArCF),148.4(br s,ArC),134.0(s,ortho-ArCH),131.4(q,J=32.4Hz,ArC-CF3),121.8(m,para-ArCH),124.8(q ,J=272.7Hz,CF3),101.3(ddd,J=32.8,24.2,3.2Hz,meta-ArCH),72.6(s,OCH2),24.8(s,CH2). 19 F NMR(376MHz,benzene-d6)δ-62.8(s,12F,CF3),-96.9(s,2F,ortho-ArCF),-108.5(s,1F,para-ArCF). 11 B NMR (160 MHz, benzene-d6) δ 13.2 (broad s).

[0221] Catalyst sample C4, bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl) THF adduct, was prepared as follows.

[0222] Preparation of lithium bis(diethyl etherate)bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)isopropoxyborate

[0223] [ka]

[0224] To a cooled (-78 °C, CO2(s) bath) solution of 1-bromo-2,6-difluorobenzene (1.46 g, 7.56 mmol) in diethyl ether (100 mL) was slowly added dropwise n-butyllithium (3.00 mL, 2.48 M in hexanes, 7.44 mmol). The reaction mixture was stirred at -78 °C for 1 h, and then a solution of bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane (3.69 g, 7.44 mmol) in ether (10 mL) was slowly added. A precipitate formed while the reaction mixture was warmed to ambient temperature. By the time the reaction mixture reached room temperature, the precipitate had dissolved, giving 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-appearing solid. The solid was dissolved in minimal boiling ether, and the solution was placed in a glovebox freezer (-33 °C). After cooling overnight, the supernatant was decanted from the crystals that had formed. The crystals were dried under vacuum. Yield: 6.85 g, 88.4%.

[0225] 1 H 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,2 H),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), 131.28(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).

[0226] Preparation of the THF adduct of bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane

[0227] [ka]

[0228] Lithium bis(diethyletherato)bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)isopropoxyborate (5.85 g, 10.6 mmol) was dissolved in ether (150 mL) and chlorotrimethylsilane (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 stirred over the weekend. By Monday, the volatiles had evaporated (unsealed container). The colorless solid was extracted with ether and filtered. The volatiles were removed under reduced pressure to give the product as a colorless solid, 4.98 g. The NMR spectrum indicated pure borane, but only about 86% of the ether required for the monoetherate complex. The product was dissolved in ether to give a cloudy solution. THF (6 mL) was added, and the solution became clear. The volatiles were removed under reduced pressure to give a glassy solid. The residue was extracted with benzene, filtered and the volatiles removed under reduced pressure to give a white solid: Yield = 4.63g, 69.9%.

[0229] 1 H NMR (400MHz, benzene-d6) δ8.02(d,J=1.8Hz,2H),7.77(dq,J=1.9,0.9Hz,1H),6. 71-6.60(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).

[0230] Catalyst sample C5, bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane, was prepared as follows.

[0231] Preparation of lithium isopropoxybis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0232] [ka]

[0233] To a cooled (-78 °C, CO2(s) bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (3.00 g, 10.24 mmol) in diethyl ether (200 mL), n-butyllithium (4.00 mL, 2.535 M in hexane, 10.14 mmol) was slowly added dropwise. The reaction mixture was stirred at -78 °C for 1 hour. Isopropoxybis(3,5-bis(trifluoromethyl)phenyl)borane (5.036 g, 10.15 mmol) in ether (18 mL) was slowly added. The reaction mixture was stirred at -78 °C for several hours. The solution was allowed to warm to ambient temperature with stirring overnight, giving a pale yellow, clear solution. The reaction mixture was stripped of volatiles to give a yellow oil. The oil was extracted with benzene. No insoluble material was found. The reaction mixture was stripped of volatiles to give a yellow oil. The yield was 7.88 g, 98.3%.

[0234] 1H NMR (400MHz, benzene e-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),135.23,133.55(t,J=4.1Hz),133.25,133.18,132.37(d,J=97.8Hz),130.92(q,J=32. 0Hz),127.80(q,J=273.9Hz),124.92(q,J=272.5Hz),124.66(q,J=272.8H z),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.

[0235] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane

[0236] [ka]

[0237] Lithium (diethyl etherato)isopropoxy-bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)-borate (7.88 g, 9.97 mmol) was dissolved in ether (150 mL). Chlorotrimethylsilane (2.6 mL, 20.5 mmol) was added. The reaction mixture was stirred overnight to give a yellow solution with a colorless precipitate. The 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 volatiles were removed under reduced pressure to give a white powder. Yield = 6.0182 g, 92.84%.

[0238] THF-free compounds: 1 H 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 B NMR (160 MHz, benzene-d6) δ 64.37.

[0239] Catalyst sample C6, (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane, was prepared as follows.

[0240] Preparation of lithium diisopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0241] [ka]

[0242] n-Butyllithium (4.00 mL, 2.535 M in hexane, 10.14 mmol) was added with stirring to a cooled (-101 °C to -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). The reaction mixture was stirred at approximately -100 °C for 2 h and then warmed to -78 °C. Bis(isopropoxy)(3,5-bis(trifluoromethyl)phenyl)borane (3.510 g, 10.26 mmol) in ether (10 mL) was slowly added. The reaction mixture was allowed to warm to ambient temperature with stirring overnight. Volatiles were removed under reduced pressure from the pale yellow, nearly clear solution to give a crystalline-looking solid. The solid was dissolved in ether (10 mL) and placed in the freezer. No precipitate was observed. 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 crop: 3.318 g. NMR analysis of the crystals showed the pure desired compound. The supernatant was placed in the freezer overnight. A crystalline material formed. The supernatant was removed with a pipette and discarded. The crystalline residue was dried under reduced pressure: 2.017 g. Total yield: 5.335 g, 82.79%.

[0243] 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. 8Hz,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). 13C NMR (101MHz, benzene-d6) δ153.10,136.65(q,J=29.6Hz),134.81(dd,J=2.7Hz,1 .9Hz),133.93(q,J=3.6Hz),131.93(q,J=31.6Hz),131.35,129.76(q,J=31.9 Hz),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. 19 F NMR (376 MHz, benzene-d6) δ -55.79, -62.66, -63.30. 11 B NMR (160 MHz, benzene-d6) δ 5.32.

[0244] Preparation of isopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane

[0245] [ka]

[0246] 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 ether (10 mL) was added chlorotrimethylsilane (2.0 mL), causing a precipitate to form rapidly. The reaction mixture was stirred overnight. The reaction mixture was filtered, and the volatiles were removed under reduced pressure. NMR analysis indicated the reaction was complete. Some presumed TMS-O-iPr ether was also present. A second crop of lithium diisopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate, prepared as above, was treated similarly (lithium salt 2.017 g, 3.17 mmol; 0.2 mL of TMSCl) and stirred for 3 h. 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 product of the first reaction. The volatiles were removed under reduced pressure. The residue was extracted with hexane, 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%.

[0247] 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). 13 C 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(d q,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. 19F 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.

[0248] Preparation of lithium isopropoxybis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borate

[0249] [ka]

[0250] To a cooled (-78 °C, CO2(s) bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (1.800 g, 6.14 mmol) in diethyl ether (150 mL), n-butyllithium (2.40 mL, 2.535 M in hexane, 6.08 mmol) was slowly added dropwise. The reaction mixture was stirred at -78 °C for 1 hour. Isopropoxy(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borane (3.022 g, 6.09 mmol) in ether (18 mL) was slowly added. The reaction mixture was stirred at -78 °C for several hours. The solution was allowed to warm to ambient temperature overnight with stirring, resulting in a pale yellow, clear solution. The reaction mixture was stripped of volatiles to give a yellow oil. The oil was extracted with benzene. No insoluble material was found. The reaction mixture was stripped of volatiles to give a yellow oil. The yield was 4.21 g, 87.6%.

[0251] 1 H 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). 13C NMR (101 MHz, benzene-d6) δ 157.17, 156.73, 134.42, 133.88 (q, J = 3.6 Hz), 133.04 (d, J = 28.4 Hz), 132.88 (q, J = 32.1 Hz), 129.95 (q, J = 31.9 Hz), 127.74 (q, J = 273.6 Hz), 127.33 (q, J = 6.9 Hz), 124.97 (q, J = 272.4 Hz), 124.50 (q, J = 273.0 Hz), 122.72 (q, J = 3.8 Hz), 118.78 (p, J = 4.1 Hz), 65.88, 65.34, 25.11, 13.91. 19 F NMR (376 MHz, benzene-d6) δ -56.31, -62.89, -63.76. 11 B NMR (160 MHz, benzene-d6) δ 2.98.

[0252] Preparation of bis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borane

[0253] [ka]

[0254] To a solution of lithium (diethyl etherato)isopropoxybis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borate (3.915 g, 4.95 mmol) in diethyl ether (150 mL) was added chlorotrimethylsilane (1.10 mL, 10.1 mmol) with stirring. A precipitate formed in the solution within 15 minutes. The reaction mixture was stirred overnight. The mixture was filtered and the volatiles removed under reduced pressure to give 3.260 g of a colorless solid. The product was extracted with hexane, filtered, and the volatiles removed under reduced pressure to give the product as a pale solid, 3.109 g, 96.53% yield.

[0255] 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). 13C NMR (126 MHz, benzene-d6) δ 141.54, 140.05, 138.35 (q, J = 3.8 Hz), 135.84 (q, J = 32.0 Hz), 133.02 (q, J = 33.0 Hz), 132.02 (q, J = 33.7 Hz), 129.98 (q, J = 3.5 Hz), 128.29, 127.91 (d, J = 2.4 Hz), 127.13 (q, J = 4.2 Hz), 124.15 (q, J = 274.2 Hz), 123.70 (q, J = 273.2 Hz), 123.37 (q, J = 273.2 Hz). 19 F NMR (470 MHz, benzene-d6) δ -56.40, -63.31, -63.58. 11 B NMR (160 MHz, benzene-d6) δ 67.58.

[0256] Catalyst sample C7 was prepared as follows.

[0257] Preparation of tris(2,5-bis(trifluoromethyl)phenyl)borane

[0258] [ka]

[0259] This reaction was carried out similarly to previously reported procedures. 2Isopropylmagnesium chloride-lithium chloride (46.0 mL, 58.0 mmol, 1.26 M solution 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 h. The reaction mixture was cooled to -78 °C, and boron trifluoride diethyl etherate (2.43 mL, 2.74 g, 19.3 mmol) in 15 mL of ether was added. The reaction mixture was allowed to warm to room temperature with stirring over the weekend. The volatiles were removed from the solution to give 12.77 g of a reddish solid. The residue was extracted with toluene and filtered. The volatiles were removed under reduced pressure to give 10.75 g of a pink powder. The solid was extracted with methylene chloride to give a light purple solution. The solution was placed in the freezer overnight. The supernatant was decanted from the very light pinkish crystalline material that formed. The filtrate was dried under reduced pressure. Yield: 7.0003 g, 55.73%. 2 Herrington, TJ; Thom, AJW; White, AJP; Ashley, AEDalton Trans. 2012, 41, 9019.

[0260] TH-free products: 1 H 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 (101 MHz, benzene-d6) δ 141.10, 136.50 (q, J = 32.2 Hz), 132.81 (q, J = 33.1 Hz), 131.59 (q, J = 3.8 Hz), 128.85 (q, J = 3.7 Hz), 127.45 (q, J = 3.4, 2.1 Hz), 123.93 (q, J = 274.6 Hz), 123.59 (q, J = 273.1 Hz). 19 F NMR (376 MHz, benzene-d6) δ -56.48, -63.77. 11 B NMR (160 MHz, benzene-d6) δ 68.81.

[0261] Catalyst sample C8, bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct, was prepared as follows.

[0262] Preparation of lithium (tetrahydrofuranate) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)isopropoxyborate

[0263] [ka]

[0264] n-Butyllithium (3.00 mL, 2.54 M in hexane, 7.61 mmol) was added to a stirred solution of 1-bromo-2,3,5,6-tetrafluoro-4-trifluoromethylbenzene (2.26 g, 7.61 mmol) in diethyl ether (100 mL) at a cooled (-101 °C to -99 °C, CO2(s) then N2(l), methanol bath) temperature. The reaction mixture was stirred at -100 °C for 2 h and then warmed to -76 °C. Bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane (3.78 g, 7.61 mmol) in ether (10 mL) was slowly added to the reaction mixture. The reaction mixture was allowed to warm slowly to ambient temperature with stirring overnight. The next day, the pale yellow, nearly clear solution was filtered, and the volatiles were removed from the filtrate under reduced pressure to give a crystalline-appearing solid. The solid was washed with hexane, filtered, and dried under reduced pressure. An aliquot of the solid was removed for NMR analysis. The solid aliquot had limited solubility in benzene. The aliquot was dissolved in THF, the volatiles removed under reduced pressure, and then re-analyzed by NMR in benzene. Yield: 6.16 g, 93.2%.

[0265] 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) δ144.07(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 -123.43(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.

[0266] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane tetrahydrofuranate, THF adduct

[0267] [ka]

[0268] To a solution of lithium (tetrahydrofuranate) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)isopropoxyborate (6.16 g, 7.10 mmol) in diethyl ether (100 mL) was added chlorotrimethylsilane (2.00 mL, 18.4 mmol) with stirring. The reaction mixture was stirred overnight. The next day, 19Analysis of an aliquot of the reaction mixture by F NMR spectroscopy revealed that no reaction had occurred. A solution of hydrogen chloride in ether (7.00 mL, 2.0 M, 14.0 mmol) was added and the reaction mixture was stirred overnight. The next day, 19 Analysis of an aliquot of the reaction mixture by F NMR spectroscopy revealed the reaction to be 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 that was dried under reduced pressure. NMR analysis of the powder revealed that one molecule of isopropanol remained in the coordination sphere of the borane. Yield as the isopropanol adduct of borane: 2.45 g, 52.8%.

[0269] A portion of the 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 yield large crystals. The supernatant was removed, and the very pale yellow crystals were washed with hexane. The crystals were dried under reduced pressure (1.08 g). The crystals were analyzed by X-ray crystallography and found to be the borane isopropanol adduct. The THF did not displace the coordinated alcohol. The supernatant solution and hexane washes from the crystals were combined and concentrated under vacuum to yield a second crop of crystals (0.422 g). This second crop of crystals was washed and dried in the same manner as the first crop. NMR analysis indicated the presence of coordinated isopropanol but little or no THF. THF was added, and then the volatiles were removed under reduced pressure. NMR analysis indicated the presence of THF, but still some isopropanol. The solid was dissolved in THF and then removed by pumping. This was repeated five more times to give the THF adduct of the product as a white powder. Yield: 0.413 g, 22.4%.

[0270] THF adduct: 1H NMR (400 MHz, benzene-d6) δ 7.87 (s, 4H), 7.80 (s, 4H), 3.02-2.93 (m, 4H), 0.78-0.72 (m, 4H). 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 .44,131.39(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. 19 F NMR (376MHz, benzene-d6) δ-56.57(t,J=21.0Hz),-62.95,-130.60(dd,J=22.5,13.2Hz),-140.71(qt,J=19.7,8.6Hz). 11 B NMR (160 MHz, benzene-d6) δ 7.22.

[0271] The catalyst samples prepared as described above in Reference Example 2 are shown below.

[0272] [ka]

[0273] The structures of fluorinated arylborane Lewis acid catalyst samples C1-C8 and a commercially available FAB are shown above. Structure C1 is tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct (corresponding to claimed starting material A1). Structure C2 is bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct (corresponding to claimed starting material A2). Structure C3 is bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct (corresponding to claimed starting material A3). Structure C4 is bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct (corresponding to claimed starting material A4). Structure C5 is bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane (corresponding to the claimed starting material A5). Structure C6 is (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane (corresponding to the claimed starting material A6). 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 claimed starting material A7).

[0274] Reference Example 3 - General Procedure In a nitrogen-purged glovebox, a 1 wt% catalyst solution was prepared in a glass vial by dissolving the above solid catalyst sample in anhydrous toluene. A cyclic polyorganohydrogensiloxane (MH-1109, D'x (x = 4, 5, 6), 11.2 g) and a Teflon-coated stir bar were placed in the glass vial. To the stirred solution, the desired catalyst sample (e.g., 225 μL) was added via micropipette, followed by the slow addition of silanol-terminated polydimethylsiloxane fluid (e.g., 8.4 g) over a period of 1 h. An aliquot of the reaction mixture was taken, quenched with one drop of phenylacetylene, and analyzed by NMR spectroscopy in CDCl3 containing Cr(acac)3 as an NMR relaxation reagent (approximately 1 g / 100 mL).29 The reaction mixture was analyzed by Si NMR. Conversion was confirmed by comparing the HOSi(Me)2O-(MOH) signal with that of MeSiO3(T). The FAB 5 ppm experiment (see Table 2) was performed on a batch scale (104.7 g of MH-1109, 80.1 g of silanol-terminated polydimethylsiloxane fluid, 105 μL of FAB in toluene) outside the glovebox on a nitrogen-purged Schlenk line using a peristaltic pump to deliver the silanol-terminated polydimethylsiloxane fluid over a 39-minute period.

[0275] Example 4 - General Procedure for Stability Monitoring In a nitrogen-purged glovebox, 1 wt. % solutions of the above catalyst samples were prepared in glass vials by dissolving the solid catalyst sample in anhydrous toluene. The glass vials contained 5 g of cyclic polyorganohydrogensiloxane (MH-1109) and a Teflon-coated stir bar. To the stirred solution, the desired catalyst sample (e.g., 100.5 μL) was added via micropipette. Aliquots were sampled over time and quenched with a phenylacetylene / toluene mixture so that toluene could act as an internal standard. The aliquots were then analyzed by GC. Relative amounts of the reaction were compared by monitoring the ratio of MH-1109 to the toluene standard. MH-1109 was monitored over time before the addition of the PA fluid. Reactions using only 5 ppm FAB were similarly carried out outside the glovebox using nitrogen-purged glass vials connected to a Schlenk line.

[0276] Dehydrogenative coupling reaction results All fluorinated triarylborane catalyst candidates tested (FAB, C1, C3, and C5) demonstrated some ability to catalyze the dehydrogenative coupling reaction shown below. However, a side reaction (ring-opening polymerization / crosslinking) occurred when using FAB and was monitored by the consumption of MH-1109 over time in the presence of the fluorinated triarylborane Lewis acid catalyst. MH-1109 was monitored over time before the addition of PA fluid. Stability tests using only a 5 ppm dose of FAB gelled immediately after measuring the 2-hour aliquot. Tests using a 100 ppm dose of FAB gelled almost immediately upon catalyst addition. All tests using one of samples C1, C3, or C5 did not gel and showed minimal signs of reaction with MH-1109 up to 24 hours after catalyst addition, an unexpected result due to the similarity of the catalyst structures. This greatly improved pot life is desirable for commercial-scale manufacturability.

[0277] [ka] Dehydrogenative Coupling Model Reaction. Note that the cyclic siloxane may have 4 to 6 siloxane units per molecule, and the corresponding cyclic groups in the product may each have 4 to 6 siloxane groups.

[0278] [Table 2] * indicates that the reaction gelled before the addition of the silanol fluid (<2 min).

[0279] Definitions and Use of Terms The abbreviations used herein have the definitions in Table 5 below.

[0280] [Table 3]

[0281] All amounts, ratios, and percentages are by weight unless otherwise indicated. The amounts of all starting materials in a composition total 100% by weight. The Summary and Abstract are incorporated herein by reference. The articles "a," "an," and "the" each refer to one or more unless otherwise indicated by the context of the specification. The singular includes the plural unless otherwise indicated. The disclosure of ranges includes the range itself and any subsumed within the range, as well as the endpoints. For example, the disclosure of a range of 2.0 to 4.0 includes not only the range 2.0 to 4.0, but also 2.1, 2.3, 3.4, 3.5, and 4.0 individually, as well as any other number subsumed within the range. Furthermore, for example, the disclosure of a range of 2.0 to 4.0 also includes subsets, such as 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7, and 3.8 to 4.0, as well as any other subset subsumed within that range. Similarly, a disclosure of a Markush group includes the group as a whole, as well as any individual members and subgroups subsumed therein. For example, a disclosure of the Markush group "a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group" includes the individual members alkyl, the subgroups alkyl and aryl, and any other individual members and subgroups subsumed within the Markush group.

[0282] The term "comprising" and its derivatives, such as "comprise" and "comprises," are used herein in their broadest sense to mean and encompass the notions of "including," "include," "consist(ing) essentially of," and "consist(ing) of." The use of "for example," "eg," "such as," and "including" to list examples does not limit the examples listed. 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.

[0283] Generally, as used herein, a hyphen "-" or a wavy line "~" in a range of values ​​means "to" or "through," ">" means "above" or "greater-than," "≥" means "at least" or "greater-than or equal to," "<" means "below" or "less-than," and "≤" means "at most" or "less-than or equal to." Each of the foregoing patent applications, patents, and / or patent publications is expressly incorporated herein by reference in its entirety on an individual basis in one or more non-limiting embodiments.

[0284] It is to be understood that the scope of the appended claims is not limited to the specific compounds, compositions, or methods described therein for purposes of describing the Detailed Description, and that variations may occur among specific embodiments within the scope of the appended claims.

Claims

1. 1. A method for preparing a product comprising a polyfunctional organohydrogensiloxane, comprising: １） A) formula, 【Chemical 1】 [In the formula, R ｏ１ , R ｏ２ , R ｏ３ , R ｏ４ , R ｏ５ , R ｏ６ , R ｍ１ , R ｍ２ , R ｍ３ , R ｍ４ , R ｍ５ , R ｍ６ , R ｐ１ , R ｐ２ , and R ｐ３ are H, F, or CF, respectively. ３ and R ２ comprises a functional group or functional polymer group, and the subscript x is 0 or 1, with the proviso that: R ｏ１ , R ｏ２ , R ｏ３ , R ｏ４ , R ｏ５ , R ｏ６ , R ｍ１ , R ｍ２ , R ｍ３ , R ｍ４ , R ｍ５ , R ｍ６ , R ｐ１ , R ｐ２ , and R ｐ３ Not all of these can be F at the same time, R ｏ１－６ , R ｍ１－６ , and R ｐ１－３ Not all of these can be H at the same time, R ｏ１ , R ｏ２ , R ｏ３ , and R ｏ４ Two or more of the above are CF ３ If R ｏ５ and R ｏ６ are each selected from H or F; B) formula, 【Chemistry 2】 wherein the subscript n is 1 to 2,000 and each R １ are independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups; and C) Formula, (RHSiO ２／２ ) ｖ wherein the subscript v is 3 to 12, and each R is an independently selected monovalent hydrocarbon radical, thereby producing a polyfunctional organohydrogensiloxane and a cyclic polyorganohydrogensiloxane of the formula: ２ preparing said product with a by-product comprising:

2. 2. The method of claim 1, wherein the fluorinated triarylborane Lewis acid is selected from the group consisting of tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct, bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct, and bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane.

3. The hydroxyl functional organosilicon compound B) comprises a hydroxyl terminated polydiorganosiloxane, the subscript n is 2 to 1,000, and each R １ is selected from the group consisting of an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, or a halogenated alkyl group of 1 to 20 carbon atoms.

4. 2. The method of claim 1, wherein in the cyclic polyorganohydrogensiloxane, subscript v is 4 to 10 and each R is an alkyl group of 1 to 6 carbon atoms.

5. 2) During and / or after step 1), the H generated during the formation of the polyfunctional organohydrogensiloxane is ２ The method of claim 1 further comprising the step of removing

6. 3) neutralizing any residual fluorinated triarylborane compound in the polyfunctional organohydrogensiloxane.

7. The polyfunctional organohydrogensiloxane is represented by the general formula a-1): 【Chemistry 3】 wherein each subscript v is independently 3 to 12, each subscript n is independently 1 to 1,000, each R is an independently selected monovalent hydrocarbon group, and each R １ are independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, provided that one or more hydrogen atoms in formula a-1) are selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, 【Chemistry 4】 [wherein each subscript n, subscript p, R, and R １ are independently selected and may be replaced with groups as described above.

8. The polyfunctional organohydrogensiloxane has the formula: 【Chemistry 5】 8. The method of claim 7, comprising:

9. 10. The method of claim 1 further comprising recovering the polyfunctional organohydrogensiloxane from the product.

10. 1. A method for preparing a clustered functional organopolysiloxane, comprising: 1) a) preparing the product by the method of any one of claims 1 to 9, and ２） a) the product, b) a hydrosilylation reaction catalyst; and c) combining starting materials comprising a reactive species having, on average, at least one aliphatically unsaturated group per molecule capable of addition reacting with silicon-bonded hydrogen atoms of starting material a), and further having, on average, one or more curable groups per molecule.

11. The reactive species is i) Formula, R ４ ｙ SiR ５ （４－ｙ） wherein the subscript y is 1 to 3 and each R ４ is an aliphatic unsaturated group capable of undergoing the addition reaction, and each R ５ is the curable group, thereby preparing a product comprising a clustered functional organosiloxane; and ii) Formula, R ６ R ７ [In the formula, each R ６ is an aliphatic unsaturated group capable of undergoing the addition reaction, and each R ７ is the curable group.

12. The clustered functional organopolysiloxane is represented by the general formula a'-1): 【Chemistry 6】 wherein each subscript v is independently 3 to 12, each subscript n is independently 1 to 1,000, each R is an independently selected monovalent hydrocarbon group, and each R １ are independently selected from monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, and each R ８ are independently selected from the group consisting of H and curable groups, with the proviso that R ８ one or more of the formula a'-2) 【Chemistry 7】 [wherein subscript n, subscript v, R, R １ , and R ８ is as defined above], provided that at least one R ８ is a curable group.

13. The clustered functional organopolysiloxane has the formula: 【Chemistry 8】 13. The method of claim 12, comprising:

14. 1. A method for preparing a curable composition, comprising: (I) a product prepared by the method according to any one of claims 1 to 13, and (II) a curing agent.

15. 1. A composition comprising: A) formula, 【Chemistry 9】 [In the formula, R ｏ１ , R ｏ２ , R ｏ３ , R ｏ４ , R ｏ５ , R ｏ６ , R ｍ１ , R ｍ２ , R ｍ３ , R ｍ４ , R ｍ５ , R ｍ６ , R ｐ１ , R ｐ２ , and R ｐ３ are H, F, or CF, respectively. ３ and R ２ comprises a functional group or functional polymer group, and the subscript x is 0 or 1, with the proviso that: R ｏ１ , R ｏ２ , R ｏ３ , R ｏ４ , R ｏ５ , R ｏ６ , R ｍ１ , R ｍ２ , R ｍ３ , R ｍ４ , R ｍ５ , R ｍ６ , R ｐ１ , R ｐ２ , and R ｐ３ Not all of these can be F at the same time, R ｏ１－６ , R ｍ１－６ , and R ｐ１－３ Not all of these can be H at the same time, R ｏ１ , R ｏ２ , R ｏ３ , and R ｏ４ Two or more of the above are CF ３ If R ｏ５ and R ｏ６ are each selected from H or F; B) formula, 【Chemistry 10】 wherein the subscript n is 1 to 2,000 and each R １ are independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups; and C) Formula, (RHSiO ２／２ ) ｖ wherein the subscript v is 3 to 12, and each R is an independently selected monovalent hydrocarbon radical, thereby providing a polyfunctional organohydrogensiloxane and a H ２ The composition of matter is prepared by preparing a product comprising a by-product comprising:

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