Method for preparing multifunctional organosiloxanes and compositions containing the same

Abstract

The present invention discloses a polyfunctional organohydrogensiloxane, which is prepared using a fluorinated triarylborane Lewis acid as a catalyst. The polyfunctional organohydrogensiloxane can be formulated into an anti-stick coating composition. Alternatively, the polyfunctional organohydrogensiloxane can be further functionalized with curable groups to form a clustered functionalized organosiloxane. The clustered functionalized organosiloxane can be formulated into a thermally free-radical curable adhesive composition.

Description

[0001] Cross - reference to related applications

[0002] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 043,152, filed on June 24, 2020, under 35 U.S.C. § 119(e). The U.S. Provisional Patent Application Serial No. 63 / 043,152 is hereby incorporated by reference. Technical field

[0003] The present invention discloses a method for preparing a polyfunctional organosiloxane. The polyfunctional organosiloxane comprises a linear polydiorganosiloxane backbone having cyclic siloxane end - capping agents. The polyfunctional organosiloxane can be used in curable compositions, for example, as a cross - linker. Background art

[0004] Methods have been proposed for preparing polyfunctional organosiloxane cross - linkers having a linear polydiorganosiloxane backbone with cyclic siloxane end - capping agents using the platinum - catalyzed reaction of cyclic polyorganohydrogensiloxanes with vinyl - terminated polydiorganosiloxanes or hydroxy - terminated polydiorganosiloxanes. These methods have the disadvantage of requiring purification of the cyclic polyorganohydrogensiloxanes, which is expensive. These methods also have the disadvantage of having poor ability to control the product structure and molecular weight. Summary of the invention

[0005] The present invention discloses a method for preparing a polyfunctional organohydrogensiloxane using a fluorinated triarylborane Lewis acid as a catalyst. The method may further include functionalizing the polyfunctional organohydrogensiloxane to form a clustered functionalized organosiloxane. The polyfunctional organohydrogensiloxane and the clustered functionalized organosiloxane can be used in curable compositions. Detailed description

[0006] The polyfunctional organohydrogensiloxane prepared by the method described herein comprises a linear polydiorganosiloxane backbone having cyclic SiH - functionalized end - capping agents. The polyfunctional organohydrogensiloxane can be used as a cross - linker. The polyfunctional organohydrogensiloxane can be used in curable compositions, such as anti - sticking coating compositions.

[0007] A method for preparing a product comprising a polyfunctional organohydrogensiloxane comprises the following steps:

[0008] 1) Combining starting materials comprising

[0009] A) A fluorinated triarylborane Lewis acid;

[0010] B) A hydroxy - functionalized organosilicon compound of the formula where each subscript n is from 1 to 2,000, and each R 1independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group; and

[0011] C) a cyclic polyorganohydrogensiloxane of the formula (RHSiO 2 / 2 ) v wherein the subscript v is from 3 to 12, and each R is a monovalent hydrocarbon group independently selected; thereby producing a product comprising a polyfunctional organohydrogensiloxane and a by-product comprising H2. The starting material in step 1) may also optionally comprise D) a solvent.

[0012] The method may also optionally include one or more additional steps. The method may also include recovering the polyfunctional organohydrogensiloxane. The method may also include: step 2) during and / or after step 1), removing the H2 generated during the formation of the polyfunctional organohydrogensiloxane and / or step 3) removing and / or neutralizing the residual triarylborane fluoride Lewis acid in the product. The by-product H2 may be removed by any convenient means such as stripping and / or combustion. The removing and / or neutralizing may be carried out by adding E) a neutralizing agent to the product and optionally subsequently filtering the product. Steps 2) and 3) may be carried out in any order. If there are particulate by-products, for example due to neutralization, the method may also include step 4) after neutralization, removing the particulates such as alumina by any convenient means such as filtration.

[0013] One or more method steps may 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, and alternatively 30 °C. Alternatively, step 1) may 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, and alternatively 30 °C. Without being bound by theory, it is believed that performing the method, particularly step 1), at a relatively low temperature (e.g., 90 °C or lower, alternatively 80 °C or lower, alternatively 70 °C or lower, and alternatively 50 °C or lower) may provide improved reaction rate, yield, or both.

[0014] The starting material used in step 1) of the method, alternatively steps 1), 2) and 3) of the method, may be free of platinum group metal catalysts. As used herein, "free of" includes none, alternatively an undetectable amount by GC, and alternatively an amount that is not sufficient to cause performance problems of an anti-stick coating prepared from an anti-stick coating composition comprising a polyfunctional organohydrogensiloxane prepared by the method described herein.

[0015] Starting material A) Catalyst

[0016] Starting material A) in the method described herein is a fluorinated triarylborane Lewis acid. The fluorinated triarylborane Lewis acid has the formula: R o is an ortho substituent, each R m is a meta substituent, and each R p is a para substituent, R 2 is optional and includes a functional group or a functional polymer group; and the subscript x is 0 or 1. In the above formula, each of R o1-6 , each of R m1-6 , and each of R p1-3 is independently selected from H, F, or CF3; provided that: not all of R o1-6 , R m1-6 , and R p1-3 can be F at the same time; not all of R o1-6 , R m1-6 , and R p1-3 can be H at the same time; and when two or more of R o1-4 are CF3, then R o5 and R o6 are each independently selected from H or F. R 2 is optional, i.e., R 2 exists when the subscript x = 1, and R 2 does not exist when the subscript x = 0. R 2 can be a Lewis base that forms a complex with the fluorinated triarylborane Lewis acid and / or a molecule or moiety containing at least one electron pair available for forming a coordinate bond with the Lewis acid, and can be as described for R 4 in paragraphs

[0024] to

[0025] of WO2019 / 055740. Examples of R 2 include cyclic ethers such as tetrahydrofuran or tetrahydropyran. Alternatively, R 2 can be tetrahydrofuran (THF).

[0017] Alternatively, each of R o1 , R o2 , R o3 , R o4 , R o5 , and R o6 can be H. Alternatively, each of R o1 , R o2 , R o3 , and R o4 can be H. Alternatively, each of R o5 and R o6 can be F.

[0018] Alternatively, each of R m1 , R m2 , Rm3 and R m4 and R m5 and R m6 Each of them can be CF3. Alternatively, R m1 and R m2 and R m3 and R m4 Each of them can be CF3. Alternatively, R m5 and R m6 Each of them can be F. Alternatively, R m5 and R m6 Each of them can be H.

[0019] Alternatively, R p1 and R p2 and R p3 Each of them can be H. Alternatively, R p1 and R p2 can be H. Alternatively, R p3 can be F. Alternatively, R p3 can be CF3.

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

[0021] Alternatively, R o1 and R o2 and R o3 and R o4 and R o5 and R o6 and R m5 and R m6 and R p1 and R p2 Each of them can be H; and R m1 and R m2 and R m3 and R m4 and R p3Each of them may be CF3. Subscript x may be 1. Alternatively, starting material A) may include bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct.

[0022] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 and R p2 each may be H; R o5 , R o6 and R p3 each may be F; and R m1 , R m2 , R m3 , R m4 each may be CF3. Subscript x may be 1. Alternatively, starting material A) may include bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct.

[0023] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 , R p2 and R p3 each may be H; R o5 and R o6 may be F; and R m1 , R m2 , R m3 and R m4 each may be CF3. Subscript x may be 1. Alternatively, starting material A) may include bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct.

[0024] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R m6 , R p1 , R p2 and R p3 each may be H; and R m1 , R m2 , R m3 , R m4 , R m5 and R o6Each of them may be CF3. Subscript x may be 0. Alternatively, starting material A) may include bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane.

[0025] Alternatively, R m1 , R p1 , R o2 , R o3 , R o4 , R p2 , R p3 , R o5 and R m6 each may be H; and R o1 , R m2 , R m3 , R m4 , R o6 and R m5 each may be CF3. Subscript x may be 0. Alternatively, starting material A) may include (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane.

[0026] Alternatively, R o1 , R o2 , R o3 , R o4 , R p1 and R p2 each may be H; R o5 , R o6 , R m5 and R m6 each may be F; and R m1 , R m2 , R m3 , R m4 and R p3 each may be CF3. Subscript x may be 1. Alternatively, starting material A) may include bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct.

[0027] Alternatively, the fluorinated triarylborane Lewis acid may be selected from 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.

[0028] Alkane Lewis acids are known in the art and can be prepared by known methods, for example, the methods disclosed in WO2019 / 055740, particularly paragraphs

[0052] to

[0096] , by changing the appropriate starting materials.

[0029] The amount of starting material A) will depend on the type and amount of the other starting materials used. However, starting material A) can be present in an amount of 5 ppm to 6000 ppm based on the combined weight of starting materials A), B), and C). Alternatively, based on the same basis, the amount can be 5 ppm to 600 ppm, alternatively 5 ppm to 500 ppm, alternatively 5 ppm to 100 ppm.

[0030] Starting material B) Hydroxy-functionalized organosilicon compound

[0031] Starting material B) is a hydroxy-functionalized organosilicon compound of formula B-1): where each subscript n is from 1 to 2,000, and each R 1 is independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups. Alternatively, the subscript n can have a value such that 2 ≤ n ≤ 2,000, alternatively 2 ≤ n ≤ 1,000, alternatively 5 ≤ n ≤ 900, alternatively 5 ≤ n ≤ 50, and alternatively 5 ≤ n ≤ 15. Alternatively, each R 1 can 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 can be independently selected from the group consisting of methyl, vinyl, phenyl, and trifluoropropyl.

[0032] When the subscript n = 1, the starting material B) can be a hydroxy-functionalized silane such as dimethyldisilanol. Hydroxy-functionalized silanes are commercially available. Alternatively, when the subscript n ≥ 2, the starting material B) can be a hydroxy-terminated polydiorganosiloxane. Suitable hydroxy-terminated polydiorganosiloxanes 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 hydroxy-terminated polydiorganosiloxane is hydroxy-terminated polydimethylsiloxane. Suitable hydroxy-terminated polydimethylsiloxanes can also be obtained commercially, for example, from Gelest, Inc. (Morrisville, Pennsylvania, USA), such as 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 a single hydroxy-functionalized organosilicon compound or a combination of two or more different hydroxy-functionalized organosilicon compounds with each other.

[0033] Starting material C) Cyclic polyorganohydrogensiloxane

[0034] The starting material C) for use in the methods described herein is a cyclic polyorganohydrogensiloxane having the formula C-1): (RHSiO 2 / 2 ) v , where the subscript v is from 3 to 12, and each R is an independently selected monovalent hydrocarbon group. Alternatively, the subscript v can be from 4 to 10, alternatively from 4 to 8. Alternatively, the subscript v can have an average value from 4 to 6, alternatively from 4 to 5, and alternatively 4. In formula C-1), R can be an alkyl group having 1 to 6 carbon atoms. Alternatively, R can be methyl, ethyl, or propyl. Alternatively, R can be methyl.

[0035] Examples of suitable cyclic polyorganohydrogensiloxanes for starting material C) include tetramethylcyclotetrasiloxane, pentamethylcyclopentasiloxane, hexamethylcyclohexasiloxane, and combinations of two or more of them. Suitable cyclic polyorganohydrogensiloxanes are known in the art and can be obtained commercially, for example, from Dow Silicones Corporation (Midland, Michigan, USA).

[0036] The amounts of starting materials B) and C) depend on various factors, including the OH content of the hydroxy-functionalized organosilicon compound of B) and the silicon-bonded hydrogen (SiH) content of the cyclic polyorganohydrogensiloxane of C). However, the amounts 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, and alternatively 5:1 to 10:1.

[0037] Starting material D) Solvent

[0038] Solvents can be used in the method. The solvents can be beneficial for introducing certain starting materials, such as starting material A) a fluorinated triarylborane Lewis acid. The solvents used herein are those that facilitate the fluidization of the starting materials but substantially do not react with any of these starting materials. The solvents can be selected based on the solubility of the starting materials and the volatility of the solvents. Solubility means that the solvent is sufficient to dissolve and / or disperse the starting materials. Volatility means the vapor pressure of the solvent.

[0039] Suitable solvents can be hydrocarbons. Suitable hydrocarbons include aromatic hydrocarbons such as benzene, toluene or xylene; and / or aliphatic hydrocarbons such as heptane, hexane or octane. Alternatively, the solvent can be a halogenated hydrocarbon such as dichloromethane, 1,1,1-trichloroethane or methylene chloride. One solvent or a combination comprising two or more solvents can be used herein.

[0040] The amount of the solvent can depend on various factors, including the type of the selected solvent and the amount and type of the other selected starting materials. However, based on the combined weight of starting materials A), B) and C), the amount of the solvent can be in the range of 0.1% to 99%, alternatively 2% to 50%.

[0041] Starting material E) Neutralizing agent

[0042] Starting material E) is a neutralizing agent, which can optionally be used to neutralize starting material A) after the product formation. Alumina, triphenylamine, triethylamine, triphenylphosphine and phenylacetylene are suitable neutralizing agents. Neutralizing agents are known in the art and can be commercially obtained, for example, from Millipore Sigma, St. Louis, Missouri, USA. The amount of the neutralizing agent depends on various factors including the amount of starting material A). However, starting material E) can be present in an amount sufficient to provide a weight ratio of the neutralizing agent to the fluorinated triarylborane Lewis acid (E:A ratio) of 1:100 to 1:1000, alternatively 1:1 to 1000:1, and alternatively 1:100 to 1:1. Alternatively, when the neutralizing agent is triphenylphosphine or phenylacetylene, the E:A ratio can be 1:1 to 20:1. Alternatively, when the neutralizing agent is alumina, the E:A ratio can be 100:1 to 1000:1.

[0043] Product of the method

[0044] The product of the above method comprises a) a polyfunctional organohydrogensiloxane and the by-product comprises H2. The product can comprise a polyfunctional organohydrogensiloxane of the general formula a-1): wherein the subscripts v and n and the groups R and R 1As described above, the prerequisite is that one or more hydrogen atoms in formula a-1) can be replaced by a group of formula a-2): wherein each of the subscript n, subscript p, R and R 1 is independently selected and as described above. Alternatively, the product may comprise a polyfunctional organohydrogensiloxane having the following unit formula a-3): [(HRSiO 2 / 2 ) v-1 (-RSiO 2 / 2 )]2[O-(R 1 2SiO 2 / 2 ) n n' [(HRSiO 2 / 2 ) v-2 (-RSiO 2 / 2 )2] o' , wherein the subscript v and n and the groups R and R 1 are as described above, the subscript o' is from 0 to 100, and the subscript n' = (o' + 1). Those skilled in the art will recognize that, depending on various factors including the relative amounts of starting materials B) and C), the product may contain more than one polyfunctional organohydrogensiloxane species. The polyfunctional organohydrogensiloxane may have more than two cyclic moieties and more than two straight-chain moieties per molecule (when o' > 0). Alternatively, the subscript v may have an average value of 5, the subscript n may have an average value of 10, the subscript n' may be from 1 to 2, and the subscript o' may be from 0 to 1. Alternatively, the subscript v may be 5, the subscript n may be 10, the subscript n' may be 2, and the subscript o' may be 1. Alternatively, when the subscript o' = 0, the product comprises a polyfunctional organohydrogensiloxane of formula a-4): wherein the subscript n and v and the groups R and R 1 are as described above.

[0045] ​Those skilled in the art will recognize that multifunctional organohydrogensiloxanes having two or more straight-chain main chains and three or more cyclic groups per molecule can also be formed and present in the product, depending on various factors including the molar ratio of starting material B) to starting material C) selected for the method. The methods described herein provide the benefit of allowing control of the multifunctional organohydrogensiloxane structure to minimize crosslinking when desired. For example, controlling the ratio of cyclic polyorganohydrogensiloxane to hydroxy-functionalized organosilicon compound can maximize the amount of multifunctional organohydrogensiloxane of formula a-1), where the subscript o' = 0, i.e., having two cyclic moieties connected via oxygen atoms at the ends of the straight-chain polydiorganosiloxane. For example, when the ratio of C) cyclic polyorganohydrogensiloxane to B) hydroxy-functionalized organosilicon compound is decreased, it is more likely to form crosslinked materials. Thus, starting materials B) and C) can be used in amounts such that the molar ratio of C:B > 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, and alternatively from 5:1 to 10:1. The described method can optionally further include recovering the multifunctional organohydrogensiloxane from the product by any convenient means such as stripping and / or distillation. The multifunctional organohydrogensiloxane produced by the above method can be used in hydrosilylation-curable compositions such as anti-stick coating compositions, for example as a crosslinking agent or co-crosslinking agent.

[0046] Method for preparing cluster-functionalized organopolysiloxanes

[0047] Alternatively, the above method can further include functionalizing the multifunctional organohydrogensiloxane to form clustered functionalized organopolysiloxanes. The above method can further include:

[0048] mixing starting materials comprising:

[0049] a) a multifunctional organohydrogensiloxane; and

[0050] b) a hydrosilylation catalyst; and

[0051] c) a reactive material having on average at least one aliphatic unsaturation per molecule capable of undergoing an addition reaction with the silicon-bonded hydrogen atoms of starting material a) multifunctional organohydrogensiloxane, wherein starting material c) further contains one or more curable groups per molecule. In short, the method can be carried out by modifying the method described in U.S. Patent 9,593,209. Starting material a) described above can be combined with the reactive material and the hydrosilylation catalyst (described as components c) and d) respectively) in the amounts and under the conditions described in columns 8, line 44 to column 10, line 47 of U.S. Patent 9,593,209.

[0052] Starting material b) Hydrosilylation catalyst

[0053] The hydrosilylation catalyst for starting material b) in the process for functionalizing a polyfunctional organohydrogensiloxane to form a clustered functionalized organopolysiloxane is known in the art and commercially available. The hydrosilylation catalyst includes platinum group metal catalysts. Such hydrosilylation catalysts can be metals selected from platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the hydrosilylation catalyst can be a compound of such metals microencapsulated in a matrix or core-shell type structure, such as tris(triphenylphosphine)rhodium(I) chloride (Wilkinson's catalyst), rhodium diphosphine chelates 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, and complexes of such compounds with low molecular weight organopolysiloxanes or platinum compounds. Complexes of platinum with low molecular weight organopolysiloxanes include the complex of platinum with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Karstedt's catalyst) and the complex of platinum with methylvinylcyclosiloxane (Ashby's catalyst). These complexes can be microencapsulated in a resin matrix. Alternatively, the hydrosilylation catalyst can include the complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane with platinum. Exemplary hydrosilylation catalysts are described in the following patents: U.S. Pat. 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 EP 0 347 895 B. Microencapsulated hydrosilylation catalysts and methods for their preparation are known in the art, as exemplified in U.S. Pat. Nos. 4,766,176 and 5,017,654. Based on the combined weight of starting materials a), b), and c), the amount used may be sufficient to provide 1 ppm to 1,000 ppm of platinum group metal.

[0054] Starting material c) Reactive substance

[0055] The reactive material of starting material c) for functionalizing a polyfunctional organohydrogensiloxane to form a clustered functionalized organopolysiloxane as described above may comprise a silane having the formula c-1): R 4 y SiR 5 (4-y) , where the subscript y is from 1 to 3, each R 4 is an aliphatic unsaturated group capable of undergoing an addition reaction, and each R 5 is an organic group containing a curable functional group. Alternatively, the subscript y can be from 1 to 2. Alternatively, the subscript y can be 1. Each R4 may be independently selected from the group consisting of alkenyl groups (such as vinyl, allyl, and hexenyl) and alkynyl groups (such as propargyl or hexynyl). Each R 5 may be independently selected from the group consisting of organic groups containing acrylate groups, alcohol groups, alkoxy groups, epoxy groups, isocyanate groups, methacrylate groups, or urethane groups. Alternatively, each R 5 may be independently selected from the group consisting of organic groups containing acrylate groups, organic groups containing epoxy groups, and organic groups containing methacrylate groups. Alternatively, each R 5 may be an organic group containing 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 combinations thereof.

[0056] Alternatively, starting material c) may comprise an organic compound that does not contain silicon atoms, for example, having the following formula c-2): R 6 R 7 , where each R 6 is an aliphatically unsaturated group capable of undergoing an addition reaction, and each R 7 is a curable group. Each R 6 may be independently selected from the group consisting of alkenyl groups (such as vinyl, allyl, and hexenyl) and alkynyl groups (such as propargyl or hexynyl). Each R 7 may be independently selected from the group consisting of organic groups containing acrylate groups, alcohol groups, alkoxy groups, epoxy groups, isocyanate groups, methacrylate groups, and urethane groups. Alternatively, each R 7 may be selected from the group consisting of organic groups containing acrylate groups, epoxy groups, and methacrylate groups. Alternatively, each R 7 may be an organic group containing 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 MilliporeSigma (St. Louis, Missouri, U.S.A.).

[0057] The starting materials used in the process for preparing the clustered functionalized organosiloxanes may optionally also contain one or more additional starting materials. The additional starting materials may be those additional components disclosed in U.S. Patent 9,593,209, column 10, line 48 to column 16, line 17. The additional starting materials are selected from the group consisting of fillers (with or without treatment agents), non-reactive resins, chain extenders, end-capping agents, and catalyst inhibitors.

[0058] The above process yields a product comprising a') a clustered functionalized organopolysiloxane or a masterbatch of a clustered functionalized organopolysiloxane with a filler and / or a non-reactive resin. The clustered functionalized organosiloxane may have the general formula a'-1): where the subscripts v, n, R, and R 1 are as described above, and where each R 8 is independently selected from the group consisting of H and curable groups, provided that one or more of the R 8 can be replaced by a group of the formula a’-2): where the subscripts n, v, R, R 1 and R 8 are as described above; provided that at least one R 8 per molecule is a curable group. Alternatively, the clustered functionalized organosiloxane may have the unit 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' , where the subscripts v, n, n', and o' and the groups R, R 1 and R 8 are as described above. Alternatively, 1 to 4 R 8 per molecule are curable groups (other than hydrogen). Alternatively, 1 to 3, alternatively 1 to 2, and alternatively on average two R 8 per molecule are curable groups (other than hydrogen). The curable groups for R 8 are derived from the above-mentioned starting material c) reactive substances. The curable groups for R 8 may be independently selected from R 4 ’ y SiR 5 (4-y) and R​6 'R 7 A group consisting of, where R 4 ' and R 6 ' are divalent hydrocarbon groups produced by the hydrosilylation reaction of the aliphatically unsaturated group of starting material c) with the silicon-bonded hydrogen atoms of starting material a). Alternatively, the subscript v can have an average value of 5, the subscript n can have an average value of 10, the subscript n' can be from 1 to 2, and the subscript o' can be from 0 to 1. Alternatively, the subscript v can be 5, the subscript n can be 10, the subscript n' can be 2, and the subscript o' can be 1. Those skilled in the art will recognize that, depending on various factors including the relative amounts of starting materials B) and C) used to prepare the organohydrogensiloxane, the product can contain more than one cluster-functionalized organosiloxane species. The cluster-functionalized organosiloxane can have more than two cyclic moieties and more than two linear moieties per molecule (when o' > 0). Alternatively, when the subscript o' = 0, the product contains a cluster-functionalized organopolysiloxane having the formula a'-2): Where R, R 1 、R 8 And the subscripts n and v are as described above.

[0059] The cluster-functionalized organosiloxane can optionally be recovered from the product by any convenient means such as stripping and / or distillation. The cluster-functionalized organosiloxane prepared as described above can be used in adhesive compositions, such as heat-radically curable adhesive compositions as additives for example.

[0060] Without being bound by theory, it is believed that a') the cluster-functionalized organosiloxane can provide one or more of the following benefits: 1) faster curing of the adhesive composition (compared to a similar adhesive composition without the above a') cluster-functionalized organosiloxane), and 2) improved tensile and elongation properties of the adhesive prepared by curing the adhesive composition, and / or 3) improved crosslinking of the adhesive composition.

[0061] Curable composition

[0062] a) The polyfunctional organohydrogensiloxane and a') the cluster-functionalized organopolysiloxane can be used in curable compositions. The curable composition can comprise:

[0063] (I) a) The polyfunctional organohydrogensiloxane, and / or a’) the cluster-functionalized organopolysiloxane;

[0064] And

[0065] (II) A curing agent.

[0066] The curing agent selected will depend on the type and amount of curable substituents on the starting material (I). For example, when a) a polyfunctional organohydrogensiloxane is included in the curable composition and / or when a') a clustered functionalized organosiloxane has an SiH functional group in addition to the curable groups introduced through starting material c) in the above methods, the curable substituent can be SiH. Alternatively, the curable substituent can be a curable group introduced by a reactive material of starting material c) used to prepare a') the clustered functionalized organosiloxane, as described above.

[0067] For example, when the starting material (I) has an SiH functional group, the curing agent (II) can be a hydrosilylation catalyst, such as those exemplified as starting material b) in the above method for functionalizing a polyfunctional organohydrogensiloxane.

[0068] For example, when the starting material (I) includes a') a clustered functionalized organosiloxane having a free-radical curable group (such as an organic group including epoxy, acrylate, or methacrylate functional groups), the curing agent can include a free-radical initiator as the curing agent (II). The free-radical initiator can be a thermal free-radical initiator, a radiation free-radical initiator, or a redox reagent. Thermal free-radical initiators include peroxides, which are known in the art and commercially available, as disclosed in U.S. Patent 9,593,209, column 16, line 49 to column 17, line 26. Based on the combined weight of all starting materials in the curable composition, the thermal free-radical initiator can be used in an amount of 0.01% to 15%, alternatively 0.1% to 5%, and alternatively 0.1% to 2%.

[0069] Alternatively, the free-radical initiator can be a radiation photoinitiator. Radiation photoinitiators are known in the art and include cationic photoinitiators such as onium salts, and radiation photoinitiators are disclosed in U.S. Patent 9,593,209, column 17, line 27 to column 18, line 40. Based on the combined weight of all starting materials in the curable composition, a suitable radiation photoinitiator can be used in the curable composition in an amount of 0.01% to 15%, alternatively 0.1% to 10%, alternatively 0.1% to 5%, and alternatively 0.1% to 2%.

[0070] Alternatively, the free-radical initiator can be a redox reagent, such as those disclosed in U.S. Patent 9,593,209, column 21, lines 33 to 53.

[0071] Alternatively, when the starting material (I) comprises a') cluster-functionalized organosiloxanes having organic groups containing OH, alkoxy or other hydrolysable groups, (II) the curing agent may comprise a condensation reaction catalyst in an amount of from 0.001% to 5% based on the combined weight of all starting materials in the curable composition. Exemplary condensation reaction catalysts are those disclosed in U.S. Patent 9,593,209, column 18, line 41 to column 19, line 15.

[0072] Alternatively, when the starting material (I) comprises a') cluster-functionalized organosiloxanes, (II) the curing agent may comprise an organoborane amine complex. Suitable organoborane amine complexes are disclosed, for example, in U.S. Patent 9,593,209, column 19, line 16 to column 21, line 33.

[0073] Alternatively, when the starting material (I) comprises a') cluster-functionalized organosiloxanes having organic groups containing isocyanate functional groups or carbamate functional groups, (II) the curing agent may comprise a compound having two or more methanol groups, such as a polyol or an amine-functionalized compound. Examples of such curing agents are disclosed in lines 54 to 63 of column 21.

[0074] Alternatively, when the starting material (I) has more than one type of curable substituent, more than one type of curing agent may be used as the starting material (II) in the curable composition. For example, when the starting material (I) has both free-radical curable groups and condensation reaction curable groups (such as epoxy groups and alkoxy groups), a combination of a free-radical initiator and a condensation reaction catalyst may be used. Alternatively, when the starting material (I) has both SiH functional groups and condensation reaction curable groups (such as alkoxy groups), a combination of a hydrosilylation reaction catalyst and a condensation reaction catalyst may be used.

[0075] The curable composition may also optionally comprise one or more additional starting materials. These are, for example, (III) crosslinking agents, (IV) solvents, (V) tackifiers, (VI) colorants, (VII) reactive diluents, (VIII) resist agents, (IX) polymerization inhibitors, (X) fillers, (XI) filler treatment agents, (XII) acid acceptors, and combinations thereof. Suitable additional starting materials are described in U.S. Patent 9,592,209, column 22, line 5 to column 29, line 8 and are exemplified as other optional components. Other additional starting materials may be added. For example, the curable composition may also optionally comprise (XIII) reactive resins and polymers, (XIV) dual-curing compounds, or both. Reactive resins and polymers for starting material (XIII) are known in the art, for example, see U.S. Patent 9,670,392, column 16, line 21 to column 18, line 35.

[0076] Thermally free-radically curable composition

[0077] The curable composition can be a thermally free-radical curable composition. The thermally free-radical curable composition can be prepared by replacing the clustered functionalized organosiloxane described as component (I) therein with the clustered functionalized organopolysiloxane prepared as described above for starting material a'). The thermally free-radical curable composition can comprise:

[0078] (I) The clustered functionalized organopolysiloxane described above as starting material a'),

[0079] (II) A curing agent, which comprises

[0080] (a) A free-radical initiator, and

[0081] (b) A condensation reaction catalyst,

[0082] (III) A crosslinking agent, and

[0083] (XIII) Reactive resins and polymers.

[0084] The thermally free-radical curable composition can further comprise (XIV) a dual-curing compound (which is an organosilicon compound having both hydrolyzable groups and free-radical reactive groups), (VIII) a resist, and (V) a tackifier, all of these starting materials being as described above.

[0085] Adhesive composition

[0086] Alternatively, the curable composition can be an adhesive composition. The adhesive composition can comprise:

[0087] A) The clustered functionalized organopolysiloxane described above as starting material a'), wherein the clustered functionalized organopolysiloxane has acrylate functional groups, epoxy functional groups, and / or methacrylate functional groups,

[0088] B) Reactive resins and polymers,

[0089] C) A condensation reaction catalyst, and

[0090] D) A free-radical initiator.

[0091] Starting material B) Reactive resins and polymers

[0092] The starting materials B) in the adhesive composition are reactive resins and polymers. The reactive resins and polymers may be the (XIII) reactive resins and polymers described above as starting materials (XIII), see U.S. Patent No. 9,670,392. Alternatively, the reactive resins and polymers may be polyalkoxy-terminated resin-polymer blends prepared as described in U.S. Provisional Patent Application Serial No. 62 / 548558 filed on August 22, 2017. The polyalkoxy-terminated resin-polymer blend comprises the reaction product of

[0093] i) a siloxane resin comprising a siloxane resin of formula (R 2 '3SiO 1 / 2 ) and (SiO 4 / 2 ) units, where each R 2 'are independently monovalent hydrocarbon groups, provided that at least one R 2 'Having an aliphatic unsaturated group, wherein the siloxane resin (R 2 '3SiO 1 / 2 ) unit (M unit) and (SiO 4 / 2 ) units (Q units) in a molar ratio in the range of 0.5:1 to 1.5:1 (M:Q ratio),

[0094] ii) a polydiorganosiloxane comprising a formula (R 2 '3SiO 1 / 2 ) ii and (R 2 '2SiO 2 / 2 ) hh Units (D units) wherein the subscript hh is 20 to 1000 and the average value of the subscript ii is 2, and

[0095] iii) an alkoxy-functionalized organohydrogensiloxane oligomer. The alkoxy-functionalized organohydrogensiloxane oligomer has a unit formula (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 , wherein each D 1 independently represents a divalent hydrocarbon group having 2 to 18 carbon atoms; each R 22 independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 18 carbon atoms (such as those described above for R 1 ), each R 23 independently is a monovalent hydrocarbon group having 1 to 18 carbon atoms (such as those described above for R 1 ), the subscript nnn is 0 or 1, the subscript ooo is 0, the values of 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 the quantity (mmm + ppp + qqq + rrr + sss + ttt + uuu + kk) ≤ 50, provided that >90 mol% of all D 1 groups in the capping agent are linear; and

[0096] iv) a hydrosilylation catalyst. Each D 1 can be, for example, an alkylene group such as ethylene, propylene, butylene or hexylene; an arylene group, such as phenylene, or an alkylarylene group such as: Alternatively, each D 1 is an alkylene group, such as ethylene or propylene; alternatively ethylene.

[0097] Starting material C) - Condensation reaction catalyst

[0098] Starting material C) in the above adhesive composition is a condensation reaction catalyst. The condensation reaction catalyst can be selected from common condensation catalysts effective for silanol-silanol condensation reactions, which include organometallic compounds, amines, and various organic and inorganic bases and acids. Organometallic compounds include organic compounds of tin, titanium, zinc, zirconium, hafnium, etc. The condensation reaction catalyst can be an organotin compound and an organotitanium compound. Exemplary organotin compounds include i) dibutyltin dilaurate, ii) dimethyltin dilaurate, iii) di-(n-butyl)bis-ketoxytin, 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) tributyltin tris(2-ethylhexanoate), xvi) dioctyltin diacetate, xvii) stannous octoate, xviii) stannous oleate, xix) stannous butyrate, xx) stannous naphthenate, xxi) dimethyltin dichloride; xxii) tin(II) diacetate, xxiii) tin(II) dioctanoate, xxiv) tin(II) 2-ethylhexanoate, 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 octoate, and xxxiv) a combination of two or more of i) to xxxiii). Exemplary organotitanium compounds can be selected from the group consisting of: i) tetra-n-butyl titanate, ii) tetra-isopropyl titanate, iii) tetra-tert-butyl titanate, iv) tetra(2-ethylhexyl) titanate, v) acetylacetonate titanate chelate, vi) ethyl acetoacetate titanate chelate, vii) triethanolamine titanate chelate, viii) tributyl titanate, and ix) a combination of two or more of i), ii), iii), iv), v), vi), vii), and viii).

[0099] The amount of the condensation reaction catalyst in the adhesive composition depends on various factors, including the choice of other starting materials, whether any additional starting materials are added, and the final use of the adhesive composition. However, based on the combined weight of all starting materials in the adhesive composition, the condensation reaction catalyst can be present in an amount in the range of 0.01% to 25%. Alternatively, the condensation reaction catalyst can 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%, alternatively 0.1% to 5%.

[0100] Starting material D) - Radical initiator

[0101] The starting material D) in the above adhesive composition is a radical initiator. The radical initiator may include azo compounds or organic peroxide compounds. Suitable azo compounds include azobenzene, azobenzene-p-sulfonic acid, azobis(dimethylvaleronitrile), 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, for example, benzoyl peroxide; dibenzoyl peroxide; 4-chlorobenzoyl peroxide; dicumyl peroxide; tert-butyl peroxybenzoate; tert-butyl cumyl peroxide; tert-butyl peroxide 2,5-dimethyl-2,5-di-tert-butylperoxyhexane; 2,4-dichlorobenzoyl peroxide; di-tert-butyl peroxide dicumyl; 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 of them.

[0102] The amount of radical initiator added to the adhesive composition depends on various factors, including the type and amount of the condensation reaction catalyst selected and the choice of other starting materials in the adhesive composition. However, based on the combined weight of all starting materials in the adhesive composition, the radical initiator may be present in an amount of 0.1% to 5%, alternatively 0.2% to 3%, alternatively 0.5% to 2%.

[0103] Additional starting materials in the adhesive composition

[0104] The above adhesive composition may further comprise one or more additional starting materials (different from the above starting materials A), B), C), and D) and added in addition to them). The additional starting materials may be selected from the group consisting of: E) dual-curing compounds, F) tackifiers, G) resistants, H) rheological modifiers, I) desiccants, J) crosslinking agents, K) fillers, L) spacers, M) acid scavengers, N) silanol-functionalized polydiorganosiloxanes, O) fluorescent optical brighteners, P) chain transfer agents, Q) (meth)acrylate monomers, R) polyalkoxy-capped polydiorganosiloxanes, S) colorants, and two or more of E), F), G), H), I), J), K), L), M), N), O), P), Q), R), and S).

[0105] Starting material E) - Dual-curing compound

[0106] The above-mentioned adhesive composition may also optionally contain starting material E) a dual-curing compound. The dual-curing compound is a silicone compound having at least one hydrolyzable group and at least one free-radical reactive group per molecule. The silicone compound for starting material E) may contain a silane of the formula R 14 mm R 22 nn SiX 4-(mm+nn) wherein R 22 As described above, R 14 is a curable group (such as an acrylate functional group, an epoxy functional group or a methacrylate functional group), X is a hydrolyzable group, the subscript mm is from 1 to 2, the subscript nn is from 0 to 2, and the amount (mm + nn) is from 2 to 3.

[0107] Each X independently represents a hydrolyzable group, which may be selected from an acetamido group, an acyloxy group (such as acetoxy), an alkoxy group, an amide group, an amino group, an aminoxy group, an oxime group, a ketoxime group, and a methylacetamido group. X is not a hydroxyl group. Alternatively, each X may be an acetoxy group or an alkoxy group. Alternatively, each X is an alkoxy group, such as methoxy, ethoxy, propoxy or butoxy; alternatively, it is methoxy.

[0108] Alternatively, the silicone compound for starting material E) may contain a polyorganosiloxane having the following 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 wherein R 22 、R 14And X and subscript mm are as described above, subscript oo ≥ 0, subscript pp ≥ 0, subscript qq ≥ 0, subscript rr ≥ 0, subscript ss ≥ 0, subscript ww ≥ 0, subscript tt ≥ 0, and subscript uu ≥ 0, provided that the quantity (oo + rr) ≥ 1, the quantity (pp + ss + ww) ≥ 1, and the quantity (oo + pp + qq + rr + ss + ww + tt + uu) > 2. Alternatively, subscript oo is from 0 to 100, alternatively from 0 to 50, alternatively from 0 to 20, alternatively from 0 to 10, alternatively from 1 to 50, alternatively from 1 to 20, and alternatively from 1 to 10. Alternatively, subscript pp can be from 0 to 100, alternatively from 0 to 50, alternatively from 0 to 20, alternatively from 0 to 10, alternatively from 1 to 50, alternatively from 1 to 20, and alternatively from 1 to 10. Alternatively, subscript qq is from 0 to 1,000, alternatively from 0 to 500, alternatively from 0 to 200, alternatively from 0 to 100, alternatively from 1 to 500, alternatively from 1 to 200, and alternatively from 1 to 100. Alternatively, subscript rr is from 0 to 100, alternatively from 0 to 50, alternatively from 0 to 20, alternatively from 0 to 10, alternatively from 1 to 50, alternatively from 1 to 20, and alternatively from 1 to 10. Alternatively, subscript ss is from 0 to 100, alternatively from 0 to 50, alternatively from 0 to 20, alternatively from 0 to 10, alternatively from 1 to 50, alternatively from 1 to 20, and alternatively from 1 to 10. Alternatively, subscript ww is from 0 to 100, alternatively from 0 to 50, alternatively from 0 to 20, alternatively from 0 to 10, alternatively from 1 to 50, alternatively from 1 to 20, and alternatively from 1 to 10. Alternatively, subscript tt is from 0 to 1,000, alternatively from 0 to 500, alternatively from 0 to 200, alternatively from 0 to 100, alternatively from 1 to 500, alternatively from 1 to 200, and alternatively from 1 to 100. Alternatively, subscript uu is from 0 to 1,000, alternatively from 0 to 500, alternatively from 0 to 200, alternatively from 0 to 100, alternatively from 1 to 500, alternatively from 1 to 200, and alternatively from 1 to 100.

[0109] Examples of starting material E) include silanes such as methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, acryloxypropylmethyldimethoxysilane, acryloxypropyldimethylmethoxysilane, and methacryloxypropyldimethylmethoxysilane.

[0110] The amount of the dual-curing compound in the adhesive composition depends on various factors, including the choice of other starting materials, whether any additional starting materials are added, and the end use of the composition. However, based on the combined weight of all the starting materials in the adhesive composition, the dual-curing compound can be present in an amount in the range of 0.01% to 25%. Alternatively, the dual-curing compound can 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%, alternatively 0.1% to 5%.

[0111] Starting material F) - Tackifier

[0112] The above adhesive composition may also optionally contain F) tackifiers. Suitable tackifiers may include transition metal chelates, alkoxysilanes (such as alkoxysilanes), combinations of alkoxysilanes and hydroxy-functionalized polyorganosiloxanes, amino-functionalized silanes, or combinations thereof. The tackifier may include a silane having the formula R 15 aaa R 16 bbb Si(OR 17 ) 4-(aaa+bbb) , where each R 15 is independently a monovalent organic group having at least 3 carbon atoms; R 16 contains at least one SiC-bonded substituent having an adhesion-promoting group (such as an amino, epoxy, mercapto, or acrylate group); each R 17 is independently a saturated hydrocarbon group, such as an alkyl group having 1 to 4 carbon atoms; the value of the subscript aaa can range from 0 to 2; the subscript bbb is 1 or 2; and the quantity (aaa + bbb) is not greater than 3. Alternatively, the tackifier may include a partial condensate of the above silanes. Alternatively, the tackifier may include a combination of an alkoxysilane and a hydroxy-functionalized polyorganosiloxane, such as trimethoxysilyl-terminated polydimethylsiloxane, which is commercially available from Dow Silicones Corporation (Midland, Michigan, USA).

[0113] Alternatively, the tackifier may include an unsaturated compound or an epoxy-functionalized compound. The tackifier may include an unsaturated alkoxysilane or an epoxy-functionalized alkoxysilane. For example, the functionalized alkoxysilane may have the formula R 18 ccc Si(OR 19 ) (4-ccc) , where the subscript ccc is 1, 2, or 3, alternatively the subscript ccc is 1. Each R 18 is independently a monovalent organic group, provided that at least one R 18 is an unsaturated organic group or an epoxy-functionalized organic group. For R18 Examples of the epoxy-functionalized organic group include 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. For R 18 Examples of the unsaturated organic group include 3-methacryloxypropyl, 3-acryloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecenyl. Each R 19 is independently a saturated hydrocarbon group having 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. Examples of R 19 include methyl, ethyl, propyl, and butyl.

[0114] Examples of suitable epoxy-functionalized 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, undecenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, and combinations thereof.

[0115] Alternatively, the tackifier may comprise an epoxy-functionalized siloxane, such as the reaction product of a hydroxy-terminated polyorganosiloxane and an epoxy-functionalized alkoxysilane as described above, or a physical blend of a hydroxy-terminated polyorganosiloxane and an epoxy-functionalized alkoxysilane. The tackifier may comprise a combination of an epoxy-functionalized alkoxysilane and an epoxy-functionalized siloxane. For example, examples of the tackifier include a mixture of 3-glycidoxypropyltrimethoxysilane and the reaction product of a hydroxy-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinyl / dimethylsiloxane copolymer.

[0116] Alternatively, the tackifier may include an amino-functionalized silane, such as an amino-functionalized alkoxysilane. Examples of amino-functionalized alkoxysilanes include: 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(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, 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, H2N(CH2)2NH(CH2)3SiCH3(OCH2CH3)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 of them.

[0117] Alternatively, the tackifier 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.

[0118] Alternatively, the tackifier may comprise a triazine-based compound having functional groups reactive with starting material A), starting material B), or starting material E) (when present), or two or more of them. The triazine ring can be mono-substituted, di-substituted, or tri-substituted, and at least one of the substituents is a reactive functional group. The functional group can be a free-radical reactive functional group or a condensation reactive functional group. Examples of triazine compounds having free-radical reactive functional groups include triallyl isocyanurate, diallylpropyl isocyanurate, tris-(methacryloyloxypropyl) isocyanurate, triallyloxy triazine, trimethacryloyloxy triazine, triacryloyl hexahydro triazine, 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.

[0119] The exact amount of the tackifier depends on various factors, including the choice and amount of other starting materials in the adhesive composition. However, based on the combined weight of all starting materials in the adhesive composition, when present, the tackifier can be added to the adhesive composition in an amount of 0.01 parts by weight to 50 parts by weight, alternatively 0.01 parts by weight to 10 parts by weight, and alternatively 0.01 parts by weight to 5 parts by weight. Examples of suitable tackifiers are described in U.S. Patent 9,156,948.

[0120] Starting material G) - Resist

[0121] The adhesive composition may also optionally contain starting material G) an anti-corrosive agent. Examples of suitable anti-corrosive agents include benzotriazole, mercaptobenzothiazole, mercaptobenzotriazole, and commercially available anti-corrosive agents such as 2-mercaptobenzothiazole from Millipore Sigma, 2,5-dimercapto-1,3,4-thiadiazole derivatives (CUVAN TM 826) and alkyl thiadiazole (CUVAN TM 484) from R.T. Vanderbilt (Norwalk, Connecticut, U.S.A.). Examples of suitable anti-corrosive agents are, for example, those described in U.S. Patent 9,156,948. When present, based on the combined weight of all starting materials in the adhesive composition, the amount of the anti-corrosive agent can be 0.05% to 0.5%.

[0122] Starting material H) - Rheology modifier

[0123] Based on the combined weight of all starting materials in the composition, the adhesive composition may also optionally contain up to 5%, alternatively 1% to 2% of starting material H) rheology modifier. 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, for example, those described in U.S. Patent 9,156,948. The amount of rheology modifier depends on various factors, including the specific rheology modifier selected and the choice of other starting materials used in the composition. However, based on the combined weight of all starting materials in the adhesive composition, the amount of rheology modifier can be from 0 parts to 20 parts, alternatively 1 part to 15 parts, and alternatively 1 part to 5 parts.

[0124] Starting material I) - Desiccant

[0125] The above composition may also optionally contain starting material I) desiccant. The desiccant binds water from various sources. For example, the desiccant can bind by-products of the condensation reaction, such as water and alcohols. Examples of suitable desiccants are disclosed, for example, in U.S. Patent 9,156,948. Examples of suitable adsorbents for the desiccant can be inorganic particles, such as zeolites such as chabazite, mordenite, and analcime; molecular sieves, such as alkali metal aluminosilicates, silica gel, silica-magnesia gel, activated carbon, activated alumina, calcium oxide, and combinations thereof. The adsorbent can have a particle size of 10 μm or less. The adsorbent can have an average pore size sufficient to adsorb water and alcohols, for example (angstroms).

[0126] Alternatively, the desiccant can bind water and / or other by-products by chemical means. A certain amount of silane crosslinker added to the composition (in addition to any silane crosslinker used as starting material J)) can act as a chemical desiccant. Without wishing to be bound by theory, it is believed that the chemical desiccant can be added to at most a dry portion of the composition to make the composition anhydrous after the various parts of the composition are mixed together. For example, alkoxysilanes suitable as desiccants include vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, isobutyltrimethoxysilane, and combinations thereof. The amount of desiccant depends on the specific desiccant selected. However, when starting material I) is a chemical desiccant, based on the combined weight of all starting materials in the composition, the amount can range from 0 parts to 15 parts, alternatively 0 parts to 10 parts, alternatively 0 parts to 5 parts, alternatively 0.1 part to 0.5 part.

[0127] Starting material J) - Crosslinking agent

[0128] The above composition may also optionally contain starting material J) a crosslinking agent. The crosslinking agent may include a silane crosslinking agent having a hydrolysable group or a partial or complete hydrolysis product thereof. The crosslinking agent has more than two substituents per molecule that react with the hydrolysable groups on starting material B). Examples of suitable silane crosslinking agents may have the general formula R 20 ddd Si(R 21 ) (4-ddd) , where each R 20 is independently a monovalent hydrocarbon group such as an alkyl group; each R 21 is a hydrolysable substituent, which may be the same group as X 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 aminooxy group, a hydroxy group, an oxime group, a ketoxime group or a methylacetamido group; and each instance of the subscript ii may be 0, 1, 2 or 3. For the silane crosslinking agent, the subscript ddd has an average value greater than 2. Alternatively, the value of the subscript ddd may range from 3 to 4. Alternatively, each R 21 may independently be selected from hydroxy, alkoxy, acetoxy, amido or oxime. Alternatively, the silane crosslinking agent may be selected from: acyloxysilanes, alkoxysilanes, ketoximesilanes and oximesilanes.

[0129] The silane crosslinking agent may include alkoxysilanes, examples of which are: dialkoxysilanes such as dialkyldialkoxysilanes; trialkoxysilanes such as alkyltrialkoxysilanes; tetraalkoxysilanes; or partial or complete hydrolysis products thereof, or another combination thereof. Examples of suitable trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, and combinations thereof, and optionally methyltrimethoxysilane. Examples of suitable tetraalkoxysilanes include tetraethoxysilane. Alternatively, the silane crosslinking agent may include acyloxysilanes such as acetoxysilanes. 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 crosslinking agent may comprise organotriacetoxysilane, for example a mixture comprising methyltriacetoxysilane and ethyltriacetoxysilane. Examples of silanes containing both alkoxy and acetoxy groups suitable for starting material J) that can be used in the composition include methyldiacetoxymethoxysilane, methylacetoxydimethoxysilane, vinyldiacetoxymethoxysilane, vinylacetoxydimethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydiethoxysilane, and combinations thereof.

[0130] Alternatively, the crosslinking agent may include an amino-functional compound such as 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(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, 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, H2N(CH2)2NH(CH2)3SiCH3(OCH2CH3)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, or combinations thereof. Examples of suitable silane crosslinking agents are disclosed in U.S. Patent 9,156,948.

[0131] Alternatively, the crosslinking agent may include a polyfunctional (meth)acrylate crosslinking agent, such as an exemplary di(meth)acrylate. Examples of such crosslinking agents are: ethylene glycol dimethacrylate, ethylene glycol diacrylate, triethylene glycol dimethacrylate, diethylene glycol bis(methacryloyloxy carbonate), polyethylene glycol diacrylate, tetraethylene glycol diacrylate, diglycerol diacrylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triglycidyl ether, trimethylolpropane tris(2-methyl-1-aziridine) propionate, trimethylolpropane triacrylate, acrylate-terminated urethane, which comprises a prepolymer, polyether diacrylate, and dimethacrylate, and combinations of two or more of them. Suitable polyfunctional (meth)acrylate crosslinking agents are disclosed, for example, in U.S. Patent 8,304,543, column 11, lines 46 to 65.

[0132] When present, the crosslinking agent may be added in an amount in the range of 0.1% to 10% based on the combined weight of all starting materials in the adhesive composition.

[0133] Starting material K) - Filler

[0134] The above composition may also optionally contain K) fillers. The fillers may include reinforcing fillers, extender fillers, conductive fillers, or combinations thereof. For example, the composition may also optionally contain the starting material (K1) reinforcing filler, which, when present, may be added in an amount in the range of 0.1% to 95%, alternatively 1% to 60%, based on the combined weight of all starting materials in the adhesive composition. The exact amount of the starting material (K1) depends on various factors, including the form of the reaction product of the composition and whether any other fillers are added. Examples of suitable reinforcing fillers include reinforcing silica fillers, such as fumed silica, silica aerosols, silica xerogels, and precipitated silica. Fumed silica is known in the art and is commercially available; for example, fumed silica sold under the trade name CAB-O-SIL by Cabot Corporation of Massachusetts, U.S.A.

[0135] Based on the combined weight of all starting materials in the adhesive composition, the adhesive composition may also optionally contain an incremental filler of starting material (K2) in an amount in the range of 0.1% to 95%, alternatively 1% to 60%, and alternatively 1% to 20%. Examples of incremental fillers include crushed quartz, alumina, magnesia, calcium carbonate (such as precipitated calcium carbonate), zinc oxide, talc, diatomaceous earth, iron oxide, clay, mica, chalk, titanium dioxide, zirconia, sandstone, carbon black, graphite, or combinations thereof. Incremental fillers are known in the art and are commercially available; such as ground silica sold under the trade name MIN-U-SIL by U.S. Silica, Berkeley Springs, WV. Suitable precipitated calcium carbonates include Winnofil TM SPM from Solvay and Ultrapflex TM and Ultrapflex TM 100. Examples of suitable fillers are disclosed in U.S. Patent 9,156,948.

[0136] Starting material L) - Spacer

[0137] The above adhesive composition may also optionally contain L) - spacers. Spacers can include organic particles, inorganic particles, or combinations thereof. Spacers can be thermally conductive, electrically conductive, or both. Spacers can have a desired particle size, for example, the particle size can be in the range of 25 μm to 125 μm. Spacers can include monodisperse beads, such as glass or polymer (e.g., polystyrene) beads. Spacers can include thermally conductive fillers, such as alumina, aluminum nitride, atomized metal powders, boron nitride, copper, and silver. The amount of spacers depends on various factors, including the particle size distribution, the pressure that will be applied during use of the composition prepared by mixing the parts or the cured product prepared therefrom, the temperature during use, and the desired thickness of the composition prepared by mixing or the cured product prepared therefrom. However, based on the combined weight of all starting materials in the composition, the composition can contain an amount of spacers in the range of 0.05% to 2%, alternatively 0.1% to 1%.

[0138] Starting material M) - Acid scavenger

[0139] The above composition may also optionally contain M) acid scavengers. Suitable acid scavengers include various inorganic and organic compounds that are essentially basic, such as magnesia, lime, and combinations thereof. Based on the combined weight of all starting materials in the composition, the composition can contain 0% to 10% of acid scavengers.

[0140] Starting material N) - Silanol-functionalized polydiorganosiloxane

[0141] The above composition may also optionally contain N) a silanol-functionalized polydiorganosiloxane. The starting material N) may comprise a polyorganosiloxane of the formula HOR 22 2SiO(R 22 2SiO) eee ((HO)R 22 SiO) fff SiR 22 2OH, a polyorganosiloxane of the formula R3SiO(R2SiO) ggg ((HO)RSiO) hhh SiR3 or a combination thereof, wherein R 22 is as described above. The subscript eee may be 0 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 0 or a positive number. Alternatively, the subscript fff may have an average value from 0 to 2000. The subscript ggg may be 0 or a positive number. Alternatively, the subscript ggg may have an average value from 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 from 2 to 2000.

[0142] The starting material N) may include polydiorganosiloxanes such as

[0143] i) hydroxyl-terminated polydimethylsiloxane,

[0144] ii) hydroxyl-terminated poly(dimethylsiloxane / methylphenylsiloxane),

[0145] iii) trimethylsilyloxy-terminated poly(dimethylsiloxane / methylhydroxysiloxane), and

[0146] iv) a combination of two or more of i), ii) and iii).

[0147] The hydroxyl-terminated polydiorganosiloxane suitable for use as the starting material N) can be prepared by methods known in the art, such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes. When added to the adhesive composition, the starting material N) may be present in an amount of 0.1% to 20%, alternatively 0.1% to 10%, and alternatively 0.1% to 5% based on the combined weight of all starting materials in the adhesive composition.

[0148] Starting material O) - Optical brightener

[0149] The above adhesive composition may also optionally contain the starting material O) an optical brightener. Suitable optical brighteners are commercially available, such as 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole), which can be TINOPAL TMObtained by OB commercial purchase. When added to the composition, the optical brightener can be present in an amount of 0.1% to 2% based on the combined weight of all starting materials in the binder composition.

[0150] Starting material P) - Chain transfer agent

[0151] The above binder composition may also optionally contain P) a chain transfer agent. When added to the binder composition, the chain transfer agent can be present in an amount of 0.01% to 5%, alternatively 0.01% to 2%, and alternatively 0.1% to 2% based on the combined weight of all starting materials in the composition.

[0152] Starting material Q) - (Meth)acrylate monomer

[0153] The above binder composition may also optionally contain starting material Q) (meth)acrylate monomers. Examples of (meth)acrylate monomers are 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 cyclohexylmethyl methacrylate. When added to the binder composition, the (meth)acrylate monomers can be present in an amount of 0.1% to 35%, alternatively 0.1% to 25%, alternatively 0.1% to 15%, and alternatively 0.1% to 10% based on the combined weight of all starting materials in the binder composition.

[0154] Starting material R) - Polyalkoxy-capped polydiorganosiloxane

[0155] Except for any starting materials prepared by preparing the above starting material B), starting material R) is a polyalkoxy-terminated polydiorganosiloxane. Starting material R) can be the polyalkoxy-terminated polydiorganosiloxane prepared as described above for starting material B), except that it does not contain a silicone resin. Alternatively, starting material R) can be a polyalkoxy-terminated polydiorganosiloxane prepared by a platinum-catalyzed hydrosilylation reaction.

[0156] Starting material S) - Colorant

[0157] The above binder composition may also optionally contain starting material S) a colorant. The colorant can be a dye or a pigment, such as carbon black.

[0158] When selecting starting materials for the above-described adhesive compositions, there may be an overlap between the types of starting materials because some of the starting materials described herein may have more than one function. For example, certain alkoxysilanes can be used as crosslinking agents and / or tackifiers and / or desiccants. Certain particles can be used as fillers and spacers. When additional starting materials are added to the adhesive composition, the additional starting materials are different from one another.

[0159] Method for preparing an adhesive composition

[0160] The above-described adhesive composition can be prepared by 1) mixing starting material B) i) a silicone resin and B) ii) a polydiorganosiloxane to form a B) resin polymer blend (RPB). A solvent can optionally be used to homogenize the RPB. One or more of the starting materials, such as the silicone resin, can be dissolved or dispersed in a solvent, such as those described above, for example, an aromatic hydrocarbon, such as benzene, toluene, or xylene. Based on the combined weight of all the starting materials in the adhesive composition, the amount of the solvent can be 0 to 60%, alternatively 10% to 50%, and alternatively 20% to 40%. Starting materials B) iii) and B) iv) as described above can be combined with the RPB to form a converted RPB. The method can further include: 2) combining the converted RPB with starting materials A), C), and D) by any convenient means, such as mixing. One or more additional starting materials E) to 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 method can further include heating the starting materials at a temperature of 50°C to 150°C, alternatively 60°C to 120°C, during step 1), step 2), or both. Pressure is not critical; the method can be carried out at ambient pressure.

[0161] Release coating composition

[0162] Alternatively, the curable composition can be an anti-stick coating composition. The release coating composition comprises:

[0163] (i) a polyfunctional organohydrogensiloxane prepared by the above method;

[0164] (ii) a polyorganosiloxane having, on average, at least two silicon-bonded aliphatic unsaturated groups per molecule capable of undergoing a hydrosilylation reaction,

[0165] (iii) a hydrosilylation reaction catalyst, and

[0166] (iv) a hydrosilylation reaction inhibitor.

[0167] Starting material (ii) Polyorganosiloxane having aliphatic unsaturated groups

[0168] The starting material (ii) in the anti - sticking coating composition is a polyorganosiloxane having on average at least two silicon - bonded aliphatic unsaturated groups capable of undergoing hydrosilylation reactions per molecule; alternatively, a polyorganosiloxane having on average at least two silicon - bonded groups with terminal aliphatic unsaturated groups per molecule. The polyorganosiloxane can be linear, branched, partially branched, cyclic, resinous (i.e., having a three - dimensional network), or can comprise a combination of different structures. The polyorganosiloxane can have an average formula: R 13 a SiO (4-a) / 2 ,

[0169] wherein each R 13 is independently selected from a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group, provided that in each molecule, at least two of the R 13 contain aliphatic unsaturated groups, and wherein the subscript a is chosen such that 0 < a ≤ 3.2. Suitable monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups for R 13 are as described above for R 1 . The average formula of the above - mentioned polyorganosiloxane can alternatively be written as (R 13 3SiO 1 / 2 ) b (R 13 2SiO 2 / 2 ) c (R 13 SiO 3 / 2 ) d (SiO 4 / 2 ) e , where R 13 is as defined above, and the subscripts b, c, d, and e are each independently ≥0 to ≤1, provided that the quantity (b + c + d + e)=1. Those skilled in the art understand how these M, D, T, and Q units and their mole fractions affect the subscript a in the above - mentioned average formula. T units (represented by the subscript d), Q units (represented by the subscript e), or both are typically present in polyorganosiloxane resins, while D units represented by the subscript c are typically present in polyorganosiloxane polymers (and can also be present in polyorganosiloxane resins or branched polyorganosiloxanes).

[0170] Alternatively, the starting material (i) can comprise a substantially linear, alternatively linear, polyorganosiloxane. The substantially linear polyorganosiloxane can have an average formula: R 13 a' SiO (4-a') / 2 , where each R 13 is as defined above, and wherein the subscript a' is chosen such that 1.9 ≤ a' ≤ 2.2.

[0171] At room temperature, the substantially linear polyorganosiloxane can be a flowable liquid or can have the form of an uncured rubber. The substantially linear polyorganosiloxane can have a viscosity at 25 °C of from 10 mPa·s to 30,000,000 mPa·s, or from 10 mPa·s to 10,000 mPa·s, or from 100 mPa·s to 1,000,000 mPa·s, or from 100 mPa·s to 100,000 mPa·s. The viscosity can be measured at room temperature using a Brookfield LV DV-E viscometer with a rotor selected to be suitable for the substantially linear polyorganosiloxane, i.e., a viscosity of RV-1 to RV-7.

[0172] Alternatively, when (ii) the polyorganosiloxane is substantially linear or linear, the polyorganosiloxane can have an average unit formula: (R 10 R 9 2SiO 1 / 2 ) aa (R 10 R 9 SiO 2 / 2 ) bb (R 10 2SiO 2 / 2 ) cc (R 9 3SiO 1 / 2 ) dd , where each R 9 is a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group independently selected and free of aliphatic unsaturated groups; each R 10 is independently selected from the group consisting of alkenyl and alkynyl groups; the subscript aa is 0, 1, or 2, the subscript bb is 0 or greater, the subscript cc is 1 or greater, the subscript dd is 0, 1, or 2, provided that the quantity (aa + dd) ≥ 2, and (aa + dd) = 2, provided that the quantity (aa + bb + cc + dd) is from 3 to 2,000. Alternatively, the subscript cc ≥ 0. Alternatively, the subscript bb ≥ 2. Alternatively, the quantity (aa + dd) is from 2 to 10, alternatively from 2 to 8, and alternatively from 2 to 6. Alternatively, the subscript cc is from 0 to 1,000, alternatively from 1 to 500, and alternatively from 1 to 200. Alternatively, the subscript bb is from 2 to 500, alternatively from 2 to 200, and alternatively from 2 to 100.

[0173] For R 9Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloaryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a haloaralkyl group having 7 to 12 carbon atoms, where the alkyl, aryl, and haloalkyl are as described herein. Alternatively, each R 9 is independently a monovalent hydrocarbon group free of aliphatic unsaturated groups. Alternatively, each R 9 is an alkyl group. Alternatively, each R 9 is independently methyl, ethyl, or propyl. Each instance of R 9 can be the same or different. Alternatively, each R 9 is a methyl group.

[0174] The aliphatic unsaturated monovalent hydrocarbon group for R 10 is capable of hydrosilylation reaction. Examples of suitable aliphatic unsaturated hydrocarbon groups for R 10 include alkenyl groups as defined herein, and examples are vinyl, allyl, butenyl, and hexenyl; and alkynyl groups as defined herein, and examples are ethynyl and propynyl. Alternatively, each R 10 can be vinyl or hexenyl. Alternatively, each R 10 is a vinyl group. The subscript in the above (ii-I) unit formula can have a value sufficient to make the alkenyl or alkynyl content of the branched siloxane (ii-I) be 0.1% to 1%, alternatively 0.2% to 0.5%, based on the weight of the branched siloxane (ii-I).

[0175] When the (ii) polyorganosiloxane is substantially linear, alternatively linear, at least two aliphatic unsaturated groups can be bonded to silicon atoms in side chain positions, terminal positions, or both side chain and terminal positions. As a specific example of a polyorganosiloxane having a silicon-bonded aliphatic unsaturated group in the side chain, the starting material A) can have an average unit formula: [(CH3)3SiO 1 / 2 2[(CH3)2SiO 2 / 2 cc [(CH3)ViSiO 2 / 2 bb ​​, where the subscripts bb and cc are defined as above, and Vi represents a vinyl group. For this average formula, any methyl group can be replaced by a different monovalent hydrocarbon group (such as an alkyl or aryl group), and any vinyl group can be replaced by a different aliphatically unsaturated monovalent hydrocarbon group (such as an allyl or hexenyl group). Alternatively, as a specific example of a polyorganosiloxane having at least two silicon-bonded aliphatically unsaturated groups per molecule, starting material (ii) can have the average formula: Vi(CH3)2SiO[(CH3)2SiO] cc Si(CH3)2Vi, where the subscripts cc and Vi are defined as above. The dimethylpolysiloxane capped with a silicon-bonded vinyl group can be used alone or in combination with the dimethyl, methyl-vinyl polysiloxanes directly disclosed above. For this average formula, any methyl group can be replaced by a different monovalent hydrocarbon group, and any vinyl group can be replaced by any terminal aliphatically unsaturated monovalent hydrocarbon group. Since at least two silicon-bonded aliphatically unsaturated groups can be side-chain and terminal, (ii) the polyorganosiloxane can 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, cc, and Vi are defined as above.

[0176] Examples of substantially linear polyorganosiloxanes can be illustrated by: dimethylpolysiloxane capped at both ends with dimethylvinylsilyloxy groups, methylphenylpolysiloxane capped at both ends with dimethylvinylsilyloxy groups, a copolymer of methylphenylsiloxane and dimethylsiloxane capped at both ends with dimethylvinylsilyloxy groups, a copolymer of methylvinylsiloxane and methylphenylpolysiloxane capped at both ends with dimethylvinylsilyloxy groups, a copolymer of methylvinylsiloxane and diphenylsiloxane capped at both ends with dimethylvinylsilyloxy groups, a copolymer of methylvinylsiloxane, methylphenylsiloxane and dimethylsiloxane capped at both ends with dimethylvinylsilyloxy groups, a copolymer of methylvinylsiloxane and methylphenylpolysiloxane capped at both ends with trimethylsilyloxy groups, a copolymer of methylvinylsiloxane and diphenylsiloxane capped at both ends with trimethylsilyloxy groups, and a copolymer of methylvinylsiloxane, methylphenylsiloxane and dimethylsiloxane capped at both ends with trimethylsilyloxy groups.

[0177] Alternatively, starting material (ii) can comprise a substantially linear, alternatively linear polyorganosiloxane selected from the group consisting of:

[0178] ​​i) Polydimethylsiloxane endblocked with dimethylvinylsilyloxy,

[0179] ii) Poly(dimethylsiloxane / methylvinylsiloxane) endblocked with dimethylvinylsilyloxy,

[0180] iii) Polymethylvinylsiloxane endblocked with dimethylvinylsilyloxy,

[0181] iv) Poly(dimethylsiloxane / methylvinylsiloxane) endblocked with trimethylsilyloxy,

[0182] v) Polymethylvinylsiloxane endblocked with trimethylsilyloxy,

[0183] vi) Poly(dimethylsiloxane / methylvinylsiloxane) endblocked with dimethylvinylsilyloxy,

[0184] vii) Poly(dimethylsiloxane / methylphenylsiloxane) endblocked with dimethylvinylsilyloxy,

[0185] viii) Poly(dimethylsiloxane / diphenylsiloxane) endblocked with dimethylvinylsilyloxy,

[0186] ix) Polydimethylsiloxane endblocked with phenyl, methyl, vinyl - silyloxy,

[0187] x) Polydimethylsiloxane endblocked with dimethylhexenylsilyloxy,

[0188] xi) Poly(dimethylsiloxane / methylhexenylsiloxane) endblocked with dimethylhexenylsilyloxy,

[0189] xii) Polymethylhexenylsiloxane endblocked with dimethylhexenylsilyloxy,

[0190] xiii) Poly(dimethylsiloxane / methylhexenylsiloxane) endblocked with trimethylsilyloxy,

[0191] xiv) Polymethylhexenylsiloxane endblocked with trimethylsilyloxy,

[0192] xv) Poly(dimethylsiloxane / methylhexenylsiloxane) endblocked with dimethylhexenylsilyloxy,

[0193] xvi) Poly(dimethylsiloxane / methylhexenylsiloxane) endblocked with dimethylvinylsilyloxy, and

[0194] xvii) Combinations thereof.

[0195] Alternatively, A) the polyorganosiloxane can be a resinous polyorganosiloxane. The resinous polyorganosiloxane can have the average formula: R13 a” SiO (4-a”) / 2 , where each R 13 is defined as above and where the subscript a” is chosen such that 0.5 ≤ a” ≤ 1.7.

[0196] The resinous polyorganosiloxane has a branched or three-dimensional network molecular structure. At 25 °C, the resinous polyorganosiloxane can be in liquid or solid form. Alternatively, the resinous polyorganosiloxane can be exemplified by: a polyorganosiloxane containing only T units, a polyorganosiloxane containing a combination of T units and other siloxy units (such as M, D, and / or Q siloxy units), or a polyorganosiloxane containing a combination of Q units and other siloxy units (i.e., M, D, and / or T siloxy units). Generally, the resinous polyorganosiloxane contains T and / or Q units. Specific examples of the resinous polyorganosiloxane include vinyl-terminated sesquisiloxane and vinyl-terminated MDQ resin.

[0197] Alternatively, the starting material (ii) can contain (ii-I) a branched siloxane, (ii-II) a sesquisiloxane, or both (ii-I) and (ii-II). The starting materials (ii-I) and (ii-II) can be particularly useful when the composition is to be used in anti-stick coating applications.

[0198] The starting material (ii) can be a combination of (ii-I) a branched siloxane and (ii-II) a silsesquioxane. This combination can be a physical blend or mixture. Based on the combined weight of all starting materials in the anti-stick coating composition, the branched siloxane and the silsesquioxane are present in amounts relative to each other such that the combined amounts of the (ii-I) branched siloxane and the (ii-II) silsesquioxane total 100 parts by weight. The branched siloxane can be present in an amount of 50 to 100 parts by weight, and the silsesquioxane can be present in an amount of 0 to 50 parts by weight. Alternatively, the branched siloxane can be present in an amount of 50 to 90 parts by weight, and the silsesquioxane can be present in an amount of 10 to 50 parts by weight. Alternatively, the branched siloxane can be present in an amount of 50 to 80 parts by weight, and the silsesquioxane can be present in an amount of 20 to 50 parts by weight. Alternatively, the branched siloxane can be present in an amount of 50 to 76 parts by weight, and the silsesquioxane can be present in an amount of 24 to 50 parts by weight. Alternatively, the branched siloxane can be present in an amount of 50 to 70 parts by weight, and the silsesquioxane can be present in an amount of 30 to 50 parts by weight. Without being bound by theory, it is believed that if the amount of the silsesquioxane (ii-II) exceeds 50 parts by weight in every 100 parts by weight of the combined amount of the (ii-I) branched siloxane and the (ii-II) silsesquioxane, the anti-stick coating formed from the composition may have the drawback of suffering from migration, where the silsesquioxane may migrate and contaminate the adherend, such as a pressure-sensitive adhesive in contact with the anti-stick coating.

[0199] The starting material (ii-I) branched siloxane can have 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 , where each R 9 is independently a monovalent hydrocarbon group without an aliphatic unsaturated group or a monovalent halogenated hydrocarbon group without an aliphatic unsaturated group, and each R 10 is an alkenyl group or an alkynyl group, both as described above, subscript p≥0, subscript q>0, 15≥r≥995, and subscript s>0.

[0200] In the unitary type of (ii-I), the subscript p ≥ 0. The subscript q > 0. Alternatively, the subscript q ≥ 3. The subscript r ranges from 15 to 995. The subscript s > 0. Alternatively, the subscript s ≥ 1. Alternatively, for the subscript p: 22 ≥ p ≥ 0; alternatively 20 ≥ p ≥ 0; alternatively 15 ≥ p ≥ 0; alternatively 10 ≥ p ≥ 0; and alternatively 5 ≥ p ≥ 0. Alternatively, for the subscript q: 22 ≥ q > 0; alternatively 22 ≥ q ≥ 4; alternatively 20 ≥ q > 0; alternatively 15 ≥ q > 1; alternatively 10 ≥ q ≥ 2; and alternatively 15 ≥ q ≥ 4. Alternatively, for the subscript r: 800 ≥ r ≥ 15; and alternatively 400 ≥ r ≥ 15. Alternatively, for the subscript s: 10 ≥ s > 0; alternatively, 10 ≥ s ≥ 1; alternatively 5 ≥ s > 0; and alternatively s = 1. Alternatively, the subscript s is 1 or 2. Alternatively, when the subscript s = 1, then the subscript p can be 0 and the subscript q can be 4.

[0201] The branched siloxane can comprise at least two polydiorganosiloxane chains of the formula (R 9 2SiO 2 / 2 ) m , where each subscript m is independently from 2 to 100. Alternatively, the branched siloxane can comprise at least one unit of the formula (SiO 9 2SiO 2 / 2 ) o bonded to four polydiorganosiloxane chains of the formula (R 4 / 2 ) where the subscript u is 0 or 1, each subscript t is independently from 0 to 995, alternatively from 15 to 995, and alternatively from 0 to 100, each R 11 is a monovalent hydrocarbon group independently selected, each R 9 is a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group independently selected as described above and free of aliphatic unsaturation, and each R 10 is independently selected from the group consisting of alkenyl and alkynyl groups as described above. Examples of suitable branched siloxanes for the starting material (ii-I) are those disclosed in U.S. Patent 6,806,339 and U.S. Patent Publication 2007 / 0289495.

[0202] The silsesquioxane has the unitary formula (ii-II): (R 9 3SiO 1 / 2 ) i (R 10 R 9 2SiO 1 / 2 ) f (R 9 2SiO 2 / 2 ) g (R9 SiO 3 / 2 ) h , wherein R 9 and R 10 As described above, the subscript i ≥ 0, the subscript f > 0, the subscript g is from 15 to 995, and the subscript h > 0. The subscript i can be from 0 to 10. Alternatively, for the subscript i: 12 ≥ i ≥ 0; alternatively 10 ≥ i ≥ 0; alternatively 7 ≥ i ≥ 0; alternatively 5 ≥ i ≥ 0; and alternatively 3 ≥ i ≥ 0.

[0203] Alternatively, the subscript f ≥ 1. Alternatively, the subscript f ≥ 3. Alternatively, for the subscript f: 12 ≥ f > 0; alternatively 12 ≥ f ≥ 3; alternatively 10 ≥ f > 0; alternatively 7 ≥ f > 1; alternatively 5 ≥ f ≥ 2; and alternatively 7 ≥ f ≥ 3. Alternatively, for the subscript g: 800 ≥ g ≥ 15; and alternatively 400 ≥ g ≥ 15. Alternatively, the subscript h ≥ 1. Alternatively, the subscript h is from 1 to 10. Alternatively, for the subscript h: 10 ≥ h > 0; alternatively 5 ≥ h > 0; and alternatively h = 1. Alternatively, the subscript h is from 1 to 10, alternatively the subscript h is 1 or 2. Alternatively, when the subscript h = 1, then the subscript f can be 3 and the subscript i can be 0. Based on the weight of the silsesquioxane, the value of the subscript f may be sufficient to provide a silsesquioxane of unit formula (ii-II) having an alkenyl content of 0.1% to 1%, alternatively 0.2% to 0.6%. Examples of suitable silsesquioxanes for starting material (ii) are those disclosed in U.S. Patent 4,374,967.

[0204] Starting material (ii) may comprise a combination of two or more different polyorganosiloxanes that differ in at least one property such as structure, molecular weight, content of monovalent groups bonded to silicon atoms, and content of aliphatic unsaturated groups. Based on the combined weight of all starting materials in the anti-stick coating composition, the anti-stick coating composition may comprise 60% to 98%, alternatively 60% to 95% of starting material (ii).

[0205] Starting material (iii) Hydrosilylation catalyst

[0206] The hydrosilylation catalyst used as starting material (iii) in the anti - sticking coating composition can be as described above for starting material b) and in the examples. Alternatively, the hydrosilylation catalyst for use in the anti - sticking coating composition can be selected from the group consisting of Karstedt catalyst and Ashby catalyst. (iii) The hydrosilylation catalyst is present in the anti - sticking coating composition in a catalytic amount, i.e., an amount or quantity sufficient to promote its curing under the desired conditions. The catalytic amount of the (iii) hydrosilylation catalyst can be > 0.01 ppm to 10,000 ppm; alternatively > 1,000 ppm to 5,000 ppm. Alternatively, the typical catalytic amount of the (iii) hydrosilylation catalyst is 0.1 ppm to 5,000 ppm, alternatively 1 ppm to 2,000 ppm, alternatively > 0 to 1,000 ppm. Alternatively, the catalytic amount of the (iii) hydrosilylation catalyst can be 0.01 ppm to 1,000 ppm, alternatively 0.01 ppm to 100 ppm, alternatively 20 ppm to 200 ppm, and alternatively 0.01 ppm to 50 ppm of platinum group metals; based on the combined weight of all starting materials in the anti - sticking coating composition.

[0207] Starting material (iv) Hydrosilylation inhibitor

[0208] The starting material (iv) is an inhibitor that can be used to vary the reaction rate of an anti-stick coating composition compared to a composition containing the same starting materials but omitting the inhibitor. Examples of inhibitors for hydrosilylation-curable compositions are acetylenic alcohols such as methyl butynol, 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; cycloalkenyl siloxanes such as methylvinylcyclosiloxanes, examples of which are 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrohexenylcyclotetrasiloxane and combinations thereof; enyne compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne; triazoles such as benzotriazole; phosphines; thiols; hydrazines; amines such as tetramethylethylenediamine; dialkyl fumarates, diene fumarates, dialkoxyalkyl fumarates; maleates such as diallyl maleate; nitriles; ethers; carbon monoxide; olefins such as cyclooctadiene, divinyltetramethyldisiloxane; alcohols such as benzyl alcohol; and combinations thereof. Alternatively, the hydrosilylation reaction inhibitor can be selected from the group consisting of an acetylenic alcohol (e.g., 1-ethynyl-1-cyclohexanol) and a maleate (e.g., diallyl maleate, diethyl maleate or n-propyl maleate) and combinations of two or more of them.

[0209] Alternatively, the starting material (iv) in the composition can be a silylated acetylenic compound. Without wishing to be bound by theory, it is believed that the addition of a silylated acetylenic compound reduces the yellowing of the reaction product prepared by the hydrosilylation reaction of the composition compared to the reaction product obtained by hydrosilylation of a composition that does not contain a silylated acetylenic compound or contains an organic acetylenic alcohol inhibitor (such as those described above).

[0210] Examples of silylated acetylenic compounds are (3-methyl-1-butyn-3-yloxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyn-3-yloxy)dimethylsilane, bis(3-methyl-1-butyn-3-yloxy)silane methylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyn-3-yloxy))silane, (3-methyl-1-butyn-3-yloxy)dimethylphenylsilane, (3-methyl-1-butyn-3-yloxy)dimethylhexenylsilane, (3-methyl-1-butyn-3-yloxy)triethylsilane, bis(3-methyl-1-butyn-3-yloxy)methyltrifluoropropylsilane, (3,5-dimethyl-1-hexyn-3-yloxy)trimethylsilane, (3-phenyl-1-butyn-3-yloxy)diphenylmethylsilane, (3-phenyl-1-butyn-3-yloxy)dimethylphenylsilane, (3-phenyl-1-butyn-3-yloxy)dimethylvinylsilane, (3-phenyl-1-butyn-3-yloxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-yloxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-yloxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-yloxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-yloxy)trimethylsilane, and combinations thereof. As an alternative, examples of starting material (iv) are methyl(tris(1,1-dimethyl-2-propynyloxy))silane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, or combinations thereof. The silylated acetylenic compounds that can be used as starting material (iv) can be prepared by methods known in the art, such as by reacting the above-mentioned alkynols with chlorosilanes in the presence of an acid acceptor to silylate the above-mentioned alkynols.

[0211] The amount of inhibitor added to the anti-stick coating composition will depend on a variety of factors, including the desired pot life of the composition, whether the composition will be a one-component or multi-component composition, the specific inhibitor used, and the choice and amount of starting materials (i) and (ii). However, if an inhibitor is present, the amount of inhibitor, based on the combined weight of all starting materials in the composition, can be 0% to 1%, alternatively 0% to 5%, alternatively 0.001% to 1%, alternatively 0.01% to 0.5%, and alternatively 0.0025% to 0.025%.

[0212] Additional starting materials

[0213] The anti - sticking coating composition may also optionally contain one or more additional starting materials selected from: (v) fixing additives, (vi) anti - fogging additives, (vii) anti - sticking modifiers, (viii) substantially linear or linear polyorganohydrogensiloxanes, and (ix) solvents, such as those described above for starting material D).

[0214] (v) Fixing additive

[0215] Starting material (v) is a fixing additive. Examples of suitable fixing additives are reaction products of vinylalkoxysilanes with epoxy - functionalized alkoxysilanes; reaction products of vinylacetoxysilanes with epoxy - functionalized alkoxysilanes; and combinations (e.g., physical blends and / or reaction products) of polyorganosiloxanes having at least one aliphatic unsaturated hydrocarbon group and at least one hydrolysable group per molecule (e.g., a combination of a hydroxyl - terminated vinyl - functionalized polydimethylsiloxane and glycidoxypropyltrimethoxysilane). Alternatively, the fixing additive may comprise a polyorganosilicate resin. Suitable fixing additives and their preparation methods are disclosed, for example, in U.S. Patent 9,562,149, U.S. Patent Application Publication Nos. 2003 / 0088042, 2004 / 0254274, and 2005 / 0038188, and European Patent 0556 023. The exact amount of the fixing additive depends on various factors, including the type of the substrate and whether a primer is used. However, per 100 parts by weight of starting material (ii), the amount of the fixing additive in the anti - sticking coating composition may be from 0 parts by weight to 2 parts by weight. Alternatively, the amount of the fixing additive may be from 0.01 parts by weight to 2 parts by weight per 100 parts by weight of starting material (ii).

[0216] (vi) Antifogging additive

[0217] Starting material (vi) is an anti - fogging additive, which may be added to the anti - sticking coating composition to reduce or inhibit the formation of silicone fog, especially in high - speed coating equipment during the coating process. The anti - fogging additive may be a reaction product of an organohydrogensilicon compound having at least three silicon - bonded alkenyl groups per molecule, an alkylene oxide compound, or an organovinylsiloxane with a suitable catalyst. Suitable anti - fogging additives are disclosed, for example, in U.S. Patent Application 2011 / 0287267, U.S. Patent 8,722,153, U.S. Patent 6,586,535, and U.S. Patent 5,625,023.

[0218] The amount of the anti - fogging additive will depend on various factors, including the amount and type of other starting materials selected for the anti - sticking coating composition. However, based on the combined weight of all starting materials in the anti - sticking coating composition, the amount of the anti - fogging additive may be from 0% to 10%, alternatively from 0.1% to 3%.

[0219] (vii) Anti-sticking modifier

[0220] The starting material (vii) is an anti - sticking modifier that can be added to the anti - sticking coating composition to control (reduce) the level of the peel force (the adhesive force between the anti - sticking coating and its adherend such as a label containing a pressure - sensitive adhesive). The anti - sticking coating composition with the desired peel force can be formulated from the anti - sticking coating composition without the modifier by adjusting the level of the modifier. Examples of suitable anti - sticking modifiers include trimethylsiloxy - terminated dimethylphenylmethylsiloxane copolymers. Alternatively, the anti - sticking modifier can be a condensation reaction product of an organopolysiloxane resin having a hydroxyl or alkoxy group and a diorganopolysiloxane having at least one hydroxyl or hydrolyzable group. If used, for example, 0 to 85 parts by weight, alternatively 25 to 85 parts by weight of the anti - sticking modifier can be used per 100 parts of the starting material (ii). Examples of suitable anti - sticking modifiers are disclosed, for example, in U.S. Patent 8,933,177 and U.S. Patent Application Publication 2016 / 0053056.

[0221] (viii) Linear polyorganohydrogensiloxane

[0222] The starting material (viii) is a substantially linear or linear polyorganohydrogensiloxane different from the starting material (i), which can be added as an additional cross - linker to the anti - sticking 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 2SiO 2 / 2 ) x' (R 12 3SiO 1 / 2 ) y' , where each R 12 is independently selected monovalent hydrocarbon group, the subscript v' is 0, 1 or 2, the subscript w' is 1 or greater, the subscript x' is 0 or greater, the subscript y' is 0, 1 or 2, provided that the quantity (v' + y') = 2, and the quantity (v' + w') ≥ 3. The monovalent hydrocarbon group for R 12 can be the monovalent hydrocarbon group as described above for R 1 . The quantity (v' + w' + x' + y') can be from 2 to 1,000. Examples of polyorganohydrogensiloxanes are:

[0223] i) Dimethylhydrogensiloxy - terminated poly(dimethyl / methylhydrogen)siloxane copolymer,

[0224] ii) Dimethylhydrogensiloxy - terminated polymethylhydrogensiloxane,

[0225] iii) Trimethylsilyloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymer, and

[0226] iv) Trimethylsilyloxy-terminated polymethylhydrogensiloxane, and

[0227] v) 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.).

[0228] (ix) Solvent

[0229] The starting material (x) is a solvent. Suitable solvents include the above-mentioned hydrocarbons that are starting material D) in the process for preparing polyfunctional organohydrogensiloxanes. Alternatively, the solvent can be selected from polyalkylsiloxanes, alcohols, ketones, ethylene glycol ethers, tetrahydrofuran, white spirit, naphtha, tetrahydrofuran, white spirit, or a combination thereof. Polyalkylsiloxanes having a suitable vapor pressure can be used as solvents, and these include hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyalkylsiloxanes, such as DOWSIL TM 200 fluid and DOWSIL TM OS fluid, which is commercially available from Dow Silicones Corporation (Midland, Michigan, USA.).

[0230] Alternatively, the starting material (x) can contain an organic solvent. The organic solvent can 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, or ethylene glycol n-butyl ether, tetrahydrofuran; white spirit; naphtha; or a combination thereof.

[0231] The amount of the solvent will depend on various factors, including the type of the selected solvent and the amounts and types of other starting materials selected for the anti-stick coating composition. However, based on the weight of all the starting materials in the anti-stick coating composition, the amount of the solvent can be 0% to 99%, alternatively 2% to 50%. The solvent can be added during the preparation of the anti-stick coating composition, for example, to assist in mixing and delivery. After the anti-stick coating composition is prepared, all or part of the solvent can be optionally removed.

[0232] Other optional starting materials that can also be added to the anti-stick coating compositions described herein include, for example, reactive diluents, fragrances, preservatives, colorants, and fillers such as silica, quartz, or chalk.

[0233] When selecting starting materials for the anti-stick coating compositions (and other curable compositions described herein), there can be an overlap between the types of starting materials, since certain starting materials described herein can have more than one function. Certain particles can be used as fillers and as colorants such as pigments, and even as flame retardants, such as carbon black. When additional starting materials are added to the anti-stick coating composition, the additional starting materials are different from starting materials (i) to (iv) and from each other.

[0234] Alternatively, the anti-stick coating can be free of particles or contain only a limited amount of particles (e.g., fillers and / or pigments), such as from 0 wt% to 30 wt% of the anti-stick coating composition. The particles can agglomerate or otherwise adhere to the coating machine equipment used to apply the anti-stick coating. If optical transparency is desired, they can impede the optical properties of the release coating and the release liner formed therefrom, such as transparency. The particles can be disadvantageous for adhesion to the adherend.

[0235] Alternatively, the anti-stick coating compositions of the present invention can be free of fluorinated organosilicon compounds. It is believed that during curing, fluorinated compounds can rapidly migrate to the interface between the coating composition and the substrate due to their low surface tension, such as the polyorganosiloxane anti-stick coating composition / PET film interface, and prevent the anti-stick coating (prepared by curing the anti-stick coating composition) from adhering to the substrate by creating a fluorinated barrier. By forming a barrier, fluorinated compounds can prevent any starting materials from reacting at the interface. In addition, fluorinated organosilicon compounds are generally expensive.

[0236] The anti-stick composition can be prepared by mixing the starting materials comprising (i), (ii), (iii), and (iv) above with any optional additional starting materials in any order of addition, optionally with a masterbatch, and optionally with shear.

[0237] Method for coating a substrate

[0238] A method of preparing a coated substrate with a curable composition includes disposing the curable composition on the substrate. The method further includes curing the curable composition on the substrate. Curing can be carried out by heating at an elevated temperature (e.g., 50°C to 180°C, alternatively 50°C to 120°C, and alternatively 50°C to 90°C) to obtain the coated substrate. Those skilled in the art will be able to select an appropriate temperature based on various factors, including the selection of optional starting materials in the curable composition and the substrate material of construction.

[0239] The curable composition can be set or dispensed on a substrate in any suitable manner. Generally, the curable composition is applied in wet form via wet coating techniques. 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 die coating; ix) gravure coating; x) Meyer rod coating; or xi) a combination of any two or more of i) to x). Generally, setting the curable composition on a substrate results in a wet deposit on the substrate, which is subsequently cured to obtain a coated substrate that includes a cured film formed from the curable composition on the substrate.

[0240] The substrate is not limited and can be any substrate. The cured film can be separated from the substrate or can be physically and / or chemically bonded to the substrate depending on its choice. The substrate can have an integrated hot plate or an integrated or separate furnace for curing the deposit. The substrate can optionally have continuous or discontinuous shapes, sizes, dimensions, surface roughnesses, and other properties. Alternatively, the substrate has a softening point temperature at an elevated temperature. However, the curable composition and method are not limited by this.

[0241] Alternatively, the substrate can include plastics, which can be thermosetting and / or thermoplastic. However, alternatively, the substrate can be glass, metal, paper, wood, cardboard, paperboard, silicone, or polymeric materials, or combinations thereof.

[0242] Specific examples of suitable substrates include paper blanks such as kraft paper, polyethylene-coated kraft paper (PEK-coated paper), and conventional paper; polymer substrates such as polyamide (PA); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyester; polyolefins such as polyethylene (PE), polypropylene (PP), and polybutene; styrenic resins; polyoxymethylene (POM); polycarbonate (PC); polymethyl methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); 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 resins; phenoxy resins; celluloses such as triacetyl cellulose, diacetyl cellulose, and cellophane; fluorinated resins such as polytetrafluoroethylene; thermoplastic elastomers such as polystyrene type, polyolefin type, polyurethane type, polyester type, polyamide type, polybutadiene type, polyisoprene type, and fluorine type; and copolymers and combinations thereof.

[0243] A curable composition or a wet deposit is typically cured at an elevated temperature for a period of time. This period of time is typically sufficient to effect curing of the curable composition, i.e., crosslinking. The period of time can be greater than 0 to 8 hours, alternatively greater than 0 to 2 hours, alternatively greater than 0 to 1 hour, alternatively greater than 0 to 30 minutes, alternatively greater than 0 to 15 minutes, alternatively greater than 0 to 10 minutes, alternatively greater than 0 to 5 minutes, alternatively greater than 0 to 2 minutes. The period of time depends on a variety of factors, including the elevated temperature used, the temperature selected, the desired film thickness, and the presence or absence of any water or carrier vehicle in the curable composition.

[0244] Curing the curable composition typically has a dwell time of from 0.1 second to 50 seconds, alternatively from 1 second to 10 seconds, and alternatively from 0.5 second to 30 seconds. The dwell time selected can depend on the substrate selection, the temperature selected, and the line speed. As used herein, the dwell time refers to the time that the curable composition or wet deposit is subjected to the elevated temperature. The dwell time is different from the cure time because curing may be ongoing even after the curable composition, wet deposit, or a partially cured reaction intermediate thereof is no longer subjected to the elevated temperature (i.e., typically initiating curing). Alternatively, a coated article can be prepared on a conveyor belt in an oven, and the dwell 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., in meters per second).

[0245] The period of time can be broken down into cure iterations, e.g., a first cure and a post-cure, where the first cure is, for example, 1 hour and the post-cure is, for example, 3 hours. The elevated temperature can be independently selected from any temperature above room temperature in such iterations and can be the same in each iteration.

[0246] Depending on the thicknesses and other dimensions of the film and the coated substrate, a coated substrate can be formed via an iterative process. For example, a first deposit can be formed and the first deposit can be subjected to a first elevated temperature for a first period of time to obtain a partially cured deposit. Then, a second deposit can be disposed on the partially cured deposit and the second deposit can be subjected to a second elevated temperature for a second period of time to obtain a second partially cured deposit. The partially cured deposit will also further cure for the second period of time during exposure to the second elevated temperature. A third deposit can be disposed on the second partially cured deposit and subjected to a third elevated temperature for a third period of time to obtain a third partially cured deposit. The second partially cured deposit will also further cure for the second period of time during exposure to the second elevated temperature. The process can be repeated, for example, 1 to 50 times to construct a coated article as desired. A composite consisting of the partially cured layers can be subjected to a final post-cure, for example, at the elevated temperatures and time periods described above. Each elevated temperature and time period can be independently selected and can be the same as or different from each other. When an article is formed by an iterative process, each deposit can also be independently selected and can differ in terms of the starting materials selected in the curable composition, their amounts, or both. Alternatively, in such an iterative process, each iterative layer can be fully cured rather than only partially cured.

[0247] Alternatively, the deposit can comprise a wet film. Alternatively, depending on the cure state of the partially cured layer, the iterative process can be wet-on-wet. Alternatively, the iterative process can be wet-on-dry.

[0248] The coated substrate (which includes a film formed from a curable composition on a substrate) can have different dimensions, including the relative thicknesses of the film and the substrate. The thickness of the film can vary depending on its end-use application. The thickness of the film can be greater than 0 μm to 4,000 μm, alternatively greater than 0 μm to 3,000 μm, alternatively greater than 0 μm to 2,000 μm, alternatively greater than 0 μm to 1,000 μm, alternatively greater than 0 μm to 500 μm, alternatively greater than 0 μm to 250 μm. However, other thicknesses can be envisioned, for example, 0.1 μm to 200 μm. For example, the thickness of the film can be 0.2 μm to 175 μm; alternatively 0.5 μm to 150 μm; or 0.75 μm to 100 μm; alternatively 1 μm to 75 μm; alternatively 2 μm to 60 μm; alternatively 3 μm to 50 μm; and alternatively 4 μm to 40 μm. Alternatively, when the substrate is plastic, the thickness of the film can be greater than 0 μm to 200 μm, alternatively greater than 0 μm to 150 μm, and alternatively greater than 0 μm to 100 μm.

[0249] If desired, the film can be subjected to further processing depending on the end use application of the film. For example, the film can be subjected to oxidation deposition (e.g., SiO2 deposition), resist deposition and patterning, etching, chemical, corona or plasma stripping, metallization or metal deposition processes. Such further processing techniques are generally known. Such depositions can be chemical vapor deposition (including 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 elevated temperatures, especially vacuum deposition, and the film is very suitable for such techniques given its excellent thermal stability. However, depending on the end use of the film, the film can be used with such further processing.

[0250] The coated substrate can be used in a variety of end use applications. For example, the coated substrate can be used in coating applications, packaging applications, adhesive applications, fiber applications, fabric or textile applications, building applications, transportation applications, electronic device applications or electrical applications. However, the curable composition can be used in end use applications other than the preparation of the coated substrate, for example in the preparation of articles such as silicone rubber.

[0251] Alternatively, the coated substrate can be used as a release liner, for example for tapes or adhesives, including any pressure sensitive adhesives, including acrylic type pressure sensitive adhesives, rubber type pressure sensitive adhesives and silicone type pressure sensitive adhesives, as well as acrylic type adhesives, synthetic rubber type adhesives, silicone type adhesives, epoxy resin type adhesives and polyurethane type adhesives. For double-sided tapes or adhesives, each major surface of the substrate can have a film disposed thereon.

[0252] Alternatively, when the curable composition is to be formulated as an anti-stick coating composition, the anti-stick coating composition can be prepared by mixing the starting materials together, for example to prepare a one-part composition. However, it may be desirable to prepare the anti-stick coating composition as a multi-part composition, where the starting materials having SiH functional groups (e.g., starting material (i)) and the hydrosilylation catalyst are stored in separate parts until these parts are combined at the time of use (e.g., just prior to application to the substrate).

[0253] For example, the multi-part composition can comprise:

[0254] Part (A) the matrix part, which comprises (ii) a polyorganosiloxane having on average at least 2 silicon-bonded aliphatic unsaturated hydrocarbon groups per molecule and (iii) a hydrosilylation catalyst, and one or more of a fixing additive and a solvent when present, and

[0255] Part (B) the curing agent part, which contains (ii) a polyorganosiloxane having at least 2 aliphatic unsaturated hydrocarbon groups bonded to silicon per molecule and (i) a polyfunctional organohydrogensiloxane, and when present (viii) a substantially linear or linear polyorganohydrogensiloxane, an anchoring additive, a solvent. The starting material (iv), inhibitor can be added to part (A), part (B) or both. Part (A) and part (B) can be combined in a weight ratio of (A):(B) of 1:1 to 10:1, alternatively 1:1 to 5:1, and alternatively 1:1 to 2:1. Instructions for part (A) and part (B) can be provided in a kit, such as on how to combine the parts to prepare the anti-stick coating composition, how to apply the anti-stick coating composition to a substrate and how to cure the anti-stick coating composition.

[0256] Alternatively, when an anchoring additive is present, it can be incorporated into either part (A) or part (B), or it can be added to a separate (third) part.

[0257] Alternatively, the anti-stick coating composition can be prepared by a method comprising the following steps:

[0258] 1) Mixing starting materials, which include (ii) a polyorganosiloxane having at least 2 aliphatic unsaturated hydrocarbon groups bonded to silicon per molecule, (i) a polyfunctional organohydrogensiloxane, (iii) a hydrosilylation catalyst, (iv) an inhibitor, and optionally (v) an anchoring additive, (vi) an anti-fogging additive, (vii) a controlled anti-stick agent, (viii) a linear polyorganohydrogensiloxane and (ix) a solvent, to form the anti-stick coating composition;

[0259] 2) Applying the mixture onto a substrate. Step 1) can be carried out by mixing part (A) and part (B) of the multi-part composition, as described above.

[0260] The anti-stick coating composition can be applied to a substrate, for example, by any convenient means such as spraying, knife coating, dipping, screen printing or by a roller coater (e.g., an offset web coater, a kiss coater or an engraved cylinder coater).

[0261] The anti-stick coating composition of the present invention can be applied to any substrate, such as those described above. Alternatively, the anti-stick coating composition can be applied to a polymer film substrate, such as polyester, especially polyethylene terephthalate (PET), polyethylene, polypropylene or polystyrene film. Alternatively, the anti-stick coating composition can be applied to a paper web, including plastic-coated paper (e.g., paper coated with polyethylene), cellophane, supercalendered paper or clay-coated kraft paper. Alternatively, the anti-stick coating composition can be applied to a metal foil substrate, such as aluminum foil.

[0262] The method may further include: 3) treating the substrate before applying the anti-stick coating composition. The substrate can be treated by any convenient means, such as plasma treatment or corona discharge treatment. Alternatively, the substrate can be treated by applying a primer. In some cases, the adhesion of the anti-stick coating can be improved if the substrate is treated before coating.

[0263] When the anti-stick coating composition contains a solvent, the method may further include: 4) removing the solvent, which can be carried out by any conventional means, such as heating at 50 °C to 100 °C for a time sufficient to remove all or part of the solvent. The method may further include 5) curing the anti-stick coating composition to form an anti-stick coating on the surface of the substrate. Curing can be carried out by any conventional means, such as heating at 100 °C to 200 °C.

[0264] Under the conditions of a production coater, curing can be achieved at an air temperature of 120 °C to 150 °C with a dwell time of 1 second to 6 seconds, alternatively 1.5 seconds to 3 seconds. The heating in step 4) and / or 5) can be carried out in an oven, such as an air-circulation oven or a tunnel oven, or by passing the coated film around a heated cylinder.

[0265] Examples

[0266] These examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention described in the claims. The starting materials described in Table 1 and Reference Examples 1 and 2 are used in the examples herein.

[0267] Table 1 - Starting materials

[0268]

[0269] Reference Example 1 - General procedure

[0270] Unless otherwise specified, all chemical experimental procedures and operations are carried out in a nitrogen-purged glove box or on a Schlenk line. All bulk reaction solvents (toluene, diethyl ether, hexane, tetrahydrofuran (THF)) are dried over alumina and Q5 reactive scavenger columns. All other solvents are purchased from Aldrich anhydrous grade and stored with activated molecular sieves. NMR solvents (CDCl3, CD2Cl2, and C6D6) are obtained from Cambridge Isotope Laboratories, Inc., and are passed through activated The molecular sieve was dried or, in the case of C6D6, dried using Na / K alloy. 1-Bromo-3,5-bis(trifluoromethyl)benzene, 1-bromo-2,5-bis(trifluoromethyl)benzene, 1-bromo-2,6-difluorobenzene, 1-bromo-2,4,6-trifluorobenzene, and 1-bromo-4-trifluoromethylbenzene were purchased from Oakwood Chemical. 1-Bromo-2,3,5,6-tetrafluoro-4-trifluoromethylbenzene was purchased from Alfa Aesar. FAB was purchased from TCI. All other reagents were purchased from Sigma-Aldrich and used as received. Before use, n-butyllithium (hexane solution) was titrated with a toluene solution of 1.00 M decanol using 1,10-phenanthroline as an indicator. 1

[0271] Multinuclear NMR spectra were collected on one of the following instruments: 1 H, 13 C, 19 F, 29 Si, 11 B): Varian MR-400 or Varian VNMRS-500. 11 B NMR spectra were collected only on a Varian VNMRS-500. 1 H and 13 C NMR chemical shifts were reported in parts per million relative to the residual solvent peak: 1 H - 5.32 ppm for CD2Cl2, 7.15 ppm for C6D6, 7.25 ppm for CDCl3; 13 C - 54.00 ppm for CD2Cl2, 128.00 ppm for C6D6, 77.00 ppm for CDCl3. 11 B NMR chemical shifts were referenced externally to BF3(Et2O) (0 ppm), 19 F NMR chemical shifts were referenced externally to CFCl3 (0 ppm). Reaction temperatures below ambient were measured using an Extech Instruments EasyView TM 10Dual K model EA 10 thermometer with a fine JKEM sensor PTFE wire K36INJ, except when using dry ice or ice as the sole means of cooling.

[0272] Reference Example 2 - Synthesis procedure - Preparation of starting materials

[0273] The preparation of lithium (3,5-bis(trifluoromethyl)phenyl)triisopropoxoborate (diethyl ether adduct) was carried out as follows:

[0274]

[0275] To a cold (-78 °C, CO2(s) bath) solution of 1-bromo-3,5-bis(trifluoromethyl)benzene (18.52 g, 63.19 mmol) in diethyl ether (200 mL) was added n-butyllithium (23.0 mL, 2.61 M in hexane, 60.03 mmol) with stirring. The reaction mixture was stirred at -78 °C for 3 h to form a precipitate. Triisopropyl borate (11.86 g, 63.06 mmol) in diethyl ether (20 mL) was added slowly. The reaction mixture was stirred at -78 °C for 1 h, then allowed to warm to ambient temperature and stirred for 1 h to give a slightly turbid solution. The reaction mixture was filtered and the volatiles removed under reduced pressure to give a solid. The solid was triturated with hexane, filtered, and the volatiles removed under reduced pressure to give the product as a colorless powder. Yield: 23.16 g, 94.53%. The compound was initially isolated as its ether adduct.

[0276] The preparation of (3,5-bis(trifluoromethyl)phenyl)diisopropoxyborane was carried out as follows:

[0277] 1 H NMR (500 MHz, THF-d8) δ 8.15 (s, 2H), 7.57 (s, 1H), 3.79 (p, J = 6.1 Hz, 3H), 0.95 (d, J = 6.1 Hz, 18H). 13 C NMR (126 MHz, THF-d8) δ 159.12, 134.71, 128.90 (q, J = 31.3 Hz), 125.91 (q, J = 271.8 Hz), 118.70, 67.41 (dtd, J = 44.2, 22.2, 2.9 Hz), 61.67, 26.53 (d, J = 17.7 Hz), 25.28 (dtd, J = 40.4, 20.1, 3.0 Hz). 19 F NMR (470 MHz, THF-d8) δ -63.02. 11 B NMR (160 MHz, THF-d8) δ 3.84.

[0278] To a cold (-78 °C, CO2(s) bath) solution of 1-bromo-3,5-bis(trifluoromethyl)benzene (18.52 g, 63.19 mmol) in diethyl ether (200 mL) was added n-butyllithium (23.0 mL, 2.61 M in hexane, 60.03 mmol) with stirring. The reaction mixture was stirred at -78 °C for 3 h to form a precipitate. Triisopropyl borate (11.86 g, 63.06 mmol) in diethyl ether (20 mL) was added slowly. The reaction mixture was stirred at -78 °C for 1 h, then allowed to warm to ambient temperature and stirred for 1 h to give a slightly turbid solution. The reaction mixture was filtered and the volatiles removed under reduced pressure to give a solid. The solid was triturated with hexane, filtered, and the volatiles removed under reduced pressure to give the product as a colorless powder. Yield: 23.16 g, 94.53%. The compound was initially isolated as its ether adduct.

[0279]

[0280] To a solution of lithium (diethyletherato)(3,5-bis(trifluoromethyl)phenyl)triisopropoxyborate (8.00 g, 19.6 mmol) in diethyl ether (100 mL) was added hydrochloric acid solution (12.3 mL, 2 M in ether, 24.6 mmol), and a precipitate formed immediately. The reaction mixture was stirred for two hours, filtered, and the volatiles were removed under reduced pressure. The resulting residue was extracted with hexanes, filtered, and the volatiles were removed under reduced pressure to give the product as an oil. Yield: 5.10 g, 76.1%.

[0281] 1 H NMR (500 MHz, chloroform-d) δ 8.01 (d, J = 1.9 Hz, 2H), 7.89 (dt, J = 2.0, 1.0 Hz, 1H), 4.59 (hept, J = 6.1 Hz, 1H), 1.27 (d, J = 6.2 Hz, 6H). 13 C NMR (126 MHz, chloroform-d) δ 134.19, 132.85 (td, J = 3.7, 1.9 Hz), 130.85 (q, J = 32.9 Hz), 123.67 (d, J = 272.6 Hz), 123.04 (hept, J = 3.9 Hz), 67.00, 24.58. 19 F NMR (470 MHz, chloroform-d) δ -63.34. 11 B NMR (160 MHz, chloroform-d) δ 26.66.

[0282] The preparation of lithium (diethyletherato)bis(3,5-bis(trifluoromethyl)phenyl)diisopropoxyborate was carried out as follows:

[0283]

[0284] To a cold (-78 °C, CO2(s) bath) solution of 1-bromo-3,5-bis(trifluoromethyl)benzene (4.26 g, 14.5 mmol) in diethyl ether (200 mL) under stirring was added n-butyllithium (5.30 mL, 2.61 M in hexanes, 60.0 mmol). The reaction mixture was stirred at -78 °C for 1 hour, and a precipitate formed. (3,5-Bis(trifluoromethyl)phenyl)diisopropoxyborane (4.82 g, 14.1 mmol) in ether (15 mL) was added slowly. The reaction mixture was stirred at -78 °C for 1 hour (some solid was visible), then allowed to warm to ambient temperature and stirred overnight to give a clear solution. The volatiles were removed under reduced pressure to give a crystalline solid. The solid was dissolved in hexanes, and the solution was filtered and placed in the freezer over the weekend. A large amount of crystalline material formed. The supernatant was decanted, and the volatiles were removed under reduced pressure to give a colorless crystalline material. Yield of the material: 8.23 g, 93.5%.

[0285] 1 1H NMR (400 MHz, chloroform-d) δ 7.99 (d, J = 1.9 Hz, 2H), 7.74 (dt, J = 1.8, 1.0 Hz, 1H), 3.81 (q, J = 7.1 Hz, 2H), 3.35 (hept, J = 6.1 Hz, 1H), 1.45 (t, J = 7.1 Hz, 3H), 0.78 (d, J = 6.1 Hz, 6H). 13 13C NMR (101 MHz, chloroform-d) δ 153.43, 134.19–133.42 (m), 129.51 (q, J = 31.9 Hz), 124.42 (q, J = 272.4 Hz), 119.68 (hept, J = 4.0 Hz), 66.83, 63.03, 25.48, 14.66. 19 19F NMR (376 MHz, chloroform-d) δ -63.05. 11 11B NMR (160 MHz, chloroform-d) δ 5.12.

[0286] The preparation of bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane was carried out as follows:

[0287]

[0288] To a solution of lithium bis(3,5-bis(trifluoromethyl)phenyl)diisopropoxyborate (5.00 g, 7.86 mmol) in diethyl ether (100 mL) was added a hydrochloric acid solution (5.5 mL, 2 M in ether, 11 mmol), and a precipitate immediately formed. The reaction mixture was stirred for one hour, 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% (with some residual solvent).

[0289] 1 1H 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 13C 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 19F NMR (376 MHz, chloroform-d) δ -63.33. 1111B NMR (160 MHz, chloroform-d) δ 41.80.

[0290] Synthesis procedure - Preparation of catalysts

[0291] The catalyst sample C1, tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct, was prepared as follows:

[0292] Preparation of lithium isopropoxytri(3,5-bis(trifluoromethyl)phenyl)borate

[0293]

[0294] n-Butyllithium (5.00 mL, 2.5 M in hexanes, 12.7 mmol) was slowly added dropwise to a cold (-78 °C, CO2(s) bath) solution of 1-bromo-3,5-bis(trifluoromethyl)benzene (3.76 g, 12.8 mmol) in diethyl ether (150 mL). The reaction mixture was stirred at -78 °C for 1 h. Lithium isopropoxybis(3,5-bis(trifluoromethyl)phenyl)borate (6.29 g, 12.7 mmol) in diethyl ether (10 mL) was added slowly. The reaction mixture was stirred overnight while warming to ambient temperature to give a clear, very pale yellow solution. Volatiles were removed under reduced pressure to give a crystalline solid. The solid was dissolved in the minimum of boiling diethyl ether and the solution was placed in a freezer. After cooling overnight, the supernatant was decanted from the crystals that had formed and the crystals were dried under reduced pressure to give 6.74 g. The supernatant solution was concentrated and cooled overnight in a freezer to give a second batch of crystalline material (1.54 g). Total yield: 8.28 g, 75.6%.

[0295] 1 1H NMR (400 MHz, benzene-d6) δ 8.09 (s, 6H), 7.74 (s, 3H), 3.71 (p, J = 6.1 Hz, 1H), 2.97 (q, J = 7.0 Hz, 10H), 0.70 (t, J = 7.1 Hz, 15H), 0.67 (d, J = 6.2 Hz, 6H). 13 13C 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 19F NMR (376 MHz, benzene-d6) δ -62.76. 11 11B NMR (160 MHz, benzene-d6) δ 1.56.

[0296] Preparation of Tris(3,5-bis(trifluoromethyl)phenyl)borane THF Adduct

[0297]

[0298] Trimethylchlorosilane (2.0 mL, 1.71 g, 15.8 mmol) was added to a solution of lithium isopropoxytri(3,5-bis(trifluoromethyl)phenyl)borate (6.700 g, 7.75 mmol) in diethyl ether (100 mL). The reaction mixture was stirred over the weekend. The reaction mixture was filtered and the volatiles were removed under reduced pressure to give the product as a colorless solid, 4.80 g, 95.2%.

[0299] A portion of the solid (4.041 g) was dissolved in diethyl ether (100 mL) and THF (5 mL) was added. The volatiles were removed from the reaction mixture under reduced pressure. The residue was extracted with benzene, filtered, and the volatiles were removed from the reaction mixture under reduced pressure to give the THF-adduct product as a colorless solid, 4.10 g, 91.3%.

[0300] THF Adduct: 1 H NMR (400 MHz, benzene-d6) δ 7.80–7.78 (m, 6H), 7.72 (dq, J = 1.8, 0.9 Hz, 3H), 2.90–2.83 (m, 4H), 0.57–0.49 (m, 4H). 13 C NMR (101 MHz, benzene-d6) δ 148.11, 133.40, 131.38 (q, J = 32.5 Hz), 124.21 (q, J = 272.8 Hz), 121.37 (p, J = 4.1 Hz), 74.14, 23.94 (d, J = 2.7 Hz). 19 F NMR (376 MHz, benzene-d6) δ -62.95. 11 B NMR (160 MHz, benzene-d6) δ 11.84.

[0301] The catalyst sample C2, bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct, was prepared as follows.

[0302] Preparation of Bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane

[0303]

[0304] n-Butyllithium (4.70 mL, 2.535 M in hexanes, 11.9 mmol) was added dropwise slowly to a cold (−78 °C, CO2(s) / acetone bath) solution of 1-bromo-4-trifluorotoluene (2.750 g, 12.22 mmol) in diethyl ether (200 mL). The reaction mixture was stirred at −78 °C for 3 h. Isopropoxybis(3,5-bis(trifluoromethyl)phenyl)borane (5.910 g, 11.91 mmol) in diethyl ether (15 mL) was added slowly. The reaction mixture was warmed to ambient temperature while stirring overnight to give a clear yellow solution with a trace of precipitate. The solvent was removed under reduced pressure to give a viscous yellow oil. The oil was stirred rapidly with hexanes (100 mL) overnight (some turbidity was produced). The hexane layer was decanted, filtered, and the volatiles were removed under reduced pressure. The oil layer was extracted again with hexanes and the process was repeated several times. A small amount of undissolved oil 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 trimethylchlorosilane (TMSCl, 1.5 g, 13.8 mmol) was added. A large amount of precipitate formed within 30 min. The reaction mixture was stirred overnight. The reaction mixture was filtered and the volatiles were removed under reduced pressure to give a pasty off-white sludge. NMR spectroscopy showed near complete reaction. The product was dissolved in ether and more TMSCl (0.4 mL) was added. 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 1H NMR spectroscopy still showed some isopropyl groups and some diethyl 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 mL of THF was 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%).

[0305] NMR spectrum of borane-THF complex: 1 1H NMR (400 MHz, benzene-d6) δ 7.83 (s, 4H), 7.78 (tq, J = 1.7, 0.8 Hz, 2H), 7.41 (dq, J = 7.4, 0.8 Hz, 2H), 7.07 (dq, J = 7.5, 0.9 Hz, 2H), 3.04–2.96 (m, 4H), 0.70–0.62 (m, 4H). 1313C 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 19F NMR (376 MHz, benzene-d6) δ -62.56 (s, 3F), -62.78 (s, 12F). 11 11B NMR (160 MHz, benzene-d6) δ 18.54.

[0306] The catalyst sample C3, bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct, was prepared as follows:

[0307] Preparation of lithium isopropoxy bis(diethyletherato)bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borate

[0308]

[0309] In an N2-purged glove box, 2.06 g (9.78 mmol) of 1-bromo-2,4,6-trifluorobenzene was combined 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 removal from the glove box. In the fume hood, the flask was connected to a nitrogen line and placed in a dry ice / acetone bath (-78 °C) and frozen for 20 minutes. A solution of 2.5 M n-butyllithium in hexanes (4.3 mL, 10.8 mmol) was added via syringe to the cold solution. 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 glove box and drawn into a syringe. The solution was injected into the flask containing the cold aryllithium solution at -78 °C, and the mixture was stirred at that temperature for half an hour. The dry ice / acetone bath was removed, and the reaction mixture was allowed to warm slowly to room temperature while stirring overnight. The next morning, all volatiles were removed in vacuo to give a viscous yellow solid. The flask was returned to the glove box, and the viscous 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 glove box freezer overnight (-40 °C) and a white crystalline material precipitated from the solution. The crystalline material was collected by filtration, washed with cold pentane (-40 °C), and dried in vacuo for 1 hour. Total yield: 5.29 g (impure, ~5.5 mmol of the desired lithium salt, 56%). It should be noted that pure material was not obtained; the lithium salt was contaminated with the isopropoxyborane starting material (12%-22% contaminated, depending on the batch of solid material collected). It was decided to proceed with the next step in the reaction without any further purification of the isolated material.

[0310] 1 H NMR (400 MHz, benzene-d6) δ 8.26 (s, 4H, ortho-ArCH), 7.80 (s, 2H, para-ArCH), 6.22 - 6.07 (m, 2H, ortho-ArCH), 3.68 (hept, J = 5.8 Hz, 1H, CH(CH3)2), 3.07 (q, J = 7.1 Hz, 8H, OCH2), 0.81 (t, J = 7.1 Hz, 12H, OCH2CH3), 0.67 (d, J = 6.2 Hz, 6H, CH(CH3)2). 1313C 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 = 31.9 Hz, ArC-CF3), 125.5 (q, J = 272.4 Hz, CF3), 119.9 (p, J = 4.0 Hz, para-ArCH), 101.0 (ddd, J = 36.6, 24.0, 3.7 Hz, meta-ArCH), 65.9 (s, OCH(CH3)2), 65.8 (s, OCH2CH3), 25.7 (s, OCH(CH3)2), 14.7 (s, OCH2CH3). 19 19F NMR (376 MHz, benzene-d6) δ -62.7 (s, 12F, CF3), -104.4 (br s, 2F, ortho-ArF), -112.3 (m, 1F, para-ArF).

[0311] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoro)borane

[0312]

[0313] In an N2-purged glove box, 3.30 g (78% purity, 3.29 mmol) of lithium borate salt was dissolved in 60 mL of diethyl ether to form a colorless solution (Note: The lithium borane salt was contaminated with 22% bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane). Trimethylchlorosilane (1.0 mL, 7.9 mmol) was added to the solution with stirring at room temperature. There was no immediate sign of reaction. The mixture was stirred overnight at room temperature. The next morning, a large amount of LiCl precipitate formed in the flask. An aliquot of the reaction mixture was taken and analyzed by 19 19F NMR spectroscopy to confirm the completion of the reaction. The reaction mixture was filtered through diatomaceous earth to remove LiCl, and the filtrate was aspirated to dryness. The resulting viscous white solid was extracted with 80 - 90 mL of hexane and filtered again. The hexane solution was placed in the glove box freezer overnight (-40 °C), during which 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 hour. Multinuclear NMR spectroscopy confirmed the formation of the desired substance in pure form. Yield: 0.992 g, 1.75 mmol, 53.2%.

[0314] 11H NMR (400 MHz, benzene-d6) δ 7.88 (s, 6H, ArCH on the CF3-substituted ring), 6.03 (m, 2H, ArCH on the 2,4,6-trifluorobenzene ring). 13 13C NMR (101 MHz, benzene-d6) δ 167.4 (dt, J = 257.6, 16.2 Hz, p-ArCF), 166.2 (dt, J = 253.5, 15.2 Hz, o-ArCF), 142.8 (br s, ArC), 137.5 (d, J = 3.0 Hz, o-ArCH), 132.1 (q, J = 33.4 Hz, ArC-CF3), 126.9 (pent, J = 4.0 Hz, p-ArCH), 124.1 (q, J = 273.0 Hz, CF3), 112.6 (br s, ArC), 101.6 (ddd, J = 29.0, 24.9, 3.7 Hz, m-ArCH). 19 19F NMR (376 MHz, benzene-d6) δ -63.1 (s, 12F, CF3), -92.4 (m, 2F, o-ArCF), -98.5 (s, 1F, p-ArCF). 11 11B NMR (160 MHz, benzene-d6) δ 62.9 (broad s).

[0315] Preparation of the THF Adduct of Bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoro)borane

[0316]

[0317] In an N2-purged glove box, 0.992 g (1.75 mmol) of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane was weighed into a 110 mL glass wide-mouth bottle 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-trifluoro-phenyl)borane. Yield: 0.969 g, 1.51 mmol, 86.3%.

[0318] 1 1H NMR (400 MHz, benzene-d6) δ 7.96 (s, 4H, o-ArCH), 7.79 (s, 2H, p-ArCH), 6.16 (t, J = 8.0 Hz, 2H, m-ArCH), 3.10 (m, 4H, OCH2), 0.79 (m, 4H, CH2). 1313C NMR (101 MHz, benzene-d6) δ 165.3 (ddd, J = 245.4, 17.7, 14.3 Hz, ortho-ArCF), 163.9 (dd, J = 249.5, 16.2 Hz, para-ArCF), 148.4 (brs, ArC), 134.0 (s, ortho-ArCH), 131.4 (q, J = 32.4 Hz, ArC-CF3), 121.8 (m, para-ArCH), 124.8 (q, J = 272.7 Hz, CF3), 101.3 (ddd, J = 32.8, 24.2, 3.2 Hz, meta-ArCH), 72.6 (s, OCH2), 24.8 (s, CH2). 19 19F NMR (376 MHz, benzene-d6) δ -62.8 (s, 12F, CF3), -96.9 (s, 2F, ortho-ArCF), -108.5 (s, 1F, para-ArCF). 11 11B NMR (160 MHz, benzene-d6) δ 13.2 (broad s).

[0319] The catalyst sample C4, bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)THF adduct, was prepared as follows:

[0320] Preparation of lithium bis(diethyletherato)bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)isopropoxylborate

[0321]

[0322] n-Butyllithium (3.00 mL, 2.48 M in hexanes, 7.44 mmol) was added dropwise slowly to a cold (-78 °C, CO2(s) bath) solution of 1-bromo-2,6-difluorobenzene (1.46 g, 7.56 mmol) in diethyl ether (100 mL). The reaction mixture was stirred at -78 °C for 1 h and then a solution of bis(3,5-bis(trifluoromethyl)phenyl)isopropoxylborane (3.69 g, 7.44 mmol) in diethyl ether (10 mL) was added slowly. A precipitate formed while the reaction mixture was warmed to ambient temperature. By the time the reaction mixture had 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, giving a crystalline solid. The solid was dissolved in the minimum amount of boiling diethyl ether and the solution was placed in the glovebox freezer (-33 °C). After cooling overnight, the supernatant was decanted from the crystals that had formed. The crystals were dried under reduced pressure. Yield: 6.85 g, 88.4%.

[0323] 11H NMR (400 MHz, benzene-d6) δ 8.31 (s, 4H), 7.77 (tt, J = 2.0, 0.9 Hz, 2H), 6.60 (dq, J = 8.8, 7.5 Hz, 1H), 6.47–6.41 (m, 2H), 3.71 (hept, J = 6.2 Hz, 1H), 3.05 (qd, J = 7.1, 0.7 Hz, 8H), 0.82 (td, J = 7.1, 0.6 Hz, 12H), 0.68 (d, J = 6.2 Hz, 6H). 13 13C NMR (126 MHz, benzene-d6) δ 164.45 (dd, J = 249.6, 11.3 Hz), 142.11, 137.21, 136.78 (t, J = 3.8 Hz), 135.51 (t, J = 10.8 Hz), 131.28 (q, J = 33.3 Hz), 126.10 (p, J = 3.8 Hz), 123.30 (q, J = 273.1 Hz), 111.72–111.40 (m), 73.82, 65.57, 15.11, 2.57. 19 19F NMR (376 MHz, benzene-d6) δ -62.64, -106.66. 11 11B NMR (160 MHz, benzene-d6) δ 0.68 (s).

[0324] Preparation of the THF Adduct of Bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane

[0325]

[0326] Lithium isopropoxybis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borate bis(diethyletherate) (5.85 g, 10.6 mmol) was dissolved in diethyl ether (150 mL) and trimethylchlorosilane (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 vessel). The colorless solid was extracted with diethyl ether and filtered. The volatiles were removed under reduced pressure to give the product as a colorless solid, 4.98 g. NMR spectroscopy showed pure borane but only approximately 86% of the desired diethyl ether for the monoetherate complex. The product was dissolved in diethyl ether to give a turbid solution. THF (6 mL) was added and the solution became crystal clear. The volatiles were removed under reduced pressure to give a glassy solid. The residue was extracted with benzene, filtered, and the volatiles were removed under reduced pressure to give a white solid. Yield: 4.63 g, 69.9%.

[0327] 11H NMR (400 MHz, benzene-d6) δ 8.02 (d, J = 1.8 Hz, 2H), 7.77 (dq, J = 1.9, 0.9 Hz, 1H), 6.71–6.60 (m, 0H), 6.48 (t, J = 8.4 Hz, 1H), 3.17–3.09 (m, 2H), 0.77–0.68 (m, 2H). 13 13C 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 19F NMR (376 MHz, benzene-d6) δ -62.80, -99.69 (t, J = 7.5 Hz). 11 11B NMR (160 MHz, benzene-d6) δ 12.2 (s).

[0328] The catalyst sample C5, bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane, was prepared as follows:

[0329] Preparation of lithium isopropoxybis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0330]

[0331] n-Butyllithium (4.00 mL, 2.535 M in hexanes, 10.14 mmol) was slowly added to a cold (-78 °C, CO2(s) bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (3.00 g, 10.24 mmol) in diethyl ether (200 mL). The reaction mixture was stirred at -78 °C for 1 hour. Lithium isopropoxybis(3,5-bis(trifluoromethyl)phenyl)borane (5.036 g, 10.15 mmol) in diethyl ether (18 mL) was slowly added. The reaction mixture was stirred at -78 °C for several hours. The solution was warmed to ambient temperature while stirring overnight to give a pale yellow clear solution. Volatiles were removed from the reaction mixture to give a yellow oil. The oil was extracted with benzene. There was no insoluble material. Volatiles were removed from the reaction mixture to give a yellow oil. The yield was 7.88 g, 98.3%.

[0332] 11H NMR (400 MHz, benzene-d6) δ 8.06 (s, 1H), 8.00 (s, 4H), 7.70 (dt, J = 1.8, 0.9 Hz, 2H), 7.40 (d, J = 8.3 Hz, 1H), 7.19 (d, J = 8.4 Hz, 1H), 3.79 (hept, J = 6.1 Hz, 1H), 2.78 (q, J = 7.1 Hz, 4H), 0.73 (d, J = 6.1 Hz, 6H), 0.54 (t, J = 7.1 Hz, 6H). 13 13C NMR (101 MHz, benzene-d6) δ 158.31, 153.97, 135.44 (q, J = 3.7 Hz), 135.23, 133.55 (t, J = 4.1 Hz), 133.25, 133.18, 132.37 (d, J = 97.8 Hz), 130.92 (q, J = 32.0 Hz), 127.80 (q, J = 273.9 Hz), 124.92 (q, J = 272.5 Hz), 124.66 (q, J = 272.8 Hz), 123.86 (q, J = 3.8 Hz), 119.86 (p, J = 3.9 Hz), 66.24, 66.17, 25.60, 13.94. 19 19F NMR (376 MHz, benzene-d6) δ -55.30–-55.51 (m), -62.82, -63.61. 11 11B NMR (160 MHz, benzene-d6) δ 2.16.

[0333] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane

[0334]

[0335] Lithium (diethyletherate)isopropoxy-bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate (7.88 g, 9.97 mmol) was dissolved in diethyl ether (150 mL). Trimethylchlorosilane (2.6 mL, 20.5 mmol) was added. The reaction mixture was stirred overnight to give a yellow solution with a colorless precipitate. All volatiles were removed under reduced pressure. The residue was extracted with hexane (100 ml). The mixture was filtered and the volatiles were concentrated under reduced pressure. The solution was cooled overnight in a freezer (-33 °C). The reaction mixture was filtered and the precipitate was dried under reduced pressure to give a white powder. Yield: 6.0182 g, 92.84%.

[0336] Compound without THF: 11H 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 13C NMR (126 MHz, benzene-d6) δ 140.87, 140.75, 137.49 (d, J = 3.8 Hz), 135.11 (q, J = 31.7 Hz), 133.26 (q, J = 33.0 Hz), 132.03 (q, J = 33.6 Hz), 128.29, 127.34 (q, J = 3.8 Hz), 127.11 (q, J = 4.0 Hz), 127.01 (q, J = 4.0 Hz), 124.46 (q, J = 274.3 Hz), 123.70 (q, J = 273.2 Hz), 123.49 (q, J = 272.9 Hz). 19 19F NMR (376 MHz, benzene-d6) δ -56.98, -63.43, -63.47. 11 11B NMR (160 MHz, benzene-d6) δ 64.37.

[0337] The catalyst sample C6, (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane, was prepared as follows:

[0338] Preparation of lithium diisopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0339]

[0340] Under stirring, n-butyllithium (4.00 mL, 2.535 M in hexanes, 10.14 mmol) was added to a cold (between -101 °C and -99 °C, CO2(s), then N2(l) methanol bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (3.000 g, 10.24 mmol) in diethyl ether (150 mL). The reaction mixture was stirred at about -100 °C for 2 h and then allowed to warm to -78 °C. Bis(isopropoxy)(3,5-bis(trifluoromethyl)phenyl)borane (3.510 g, 10.26 mmol) in diethyl ether (10 mL) was added slowly. The reaction mixture was allowed to warm to ambient temperature while stirring overnight. Volatiles were removed from the pale yellow almost clear solution under reduced pressure to give a crystalline solid. The solid was dissolved in diethyl ether (10 mL) and placed in a freezer. No precipitate formed. The diethyl ether was evaporated and the yellow solid was dissolved in hexanes, filtered and concentrated under a stream of nitrogen to give a crystalline solid. The supernatant was removed and the solid was dried under reduced pressure. Yield of colorless crystals from the first batch: 3.318 g. NMR analysis of the crystals showed the pure desired compound. The supernatant was placed in a freezer overnight. Crystalline material formed. The supernatant was decanted and discarded. The crystalline residue was dried under reduced pressure: 2.017 g. Total yield: 5.335 g, 82.79%.

[0341] 1 H NMR (400 MHz, benzene-d6) δ 8.39 (s, 2H), 8.26 (s, 1H), 7.90 (dq, J = 1.8, 0.9 Hz, 1H), 7.56 (d, J = 8.2 Hz, 1H), 7.27 (ddt, J = 7.9, 1.7, 0.8 Hz, 1H), 3.18 (hept, J = 6.0 Hz, 2H), 2.92 (q, J = 7.1 Hz, 4H), 0.89 (t, J = 7.1 Hz, 6H), 0.78 (d, J = 6.1 Hz, 6H), 0.68 (d, J = 6.0 Hz, 6H). 13 C NMR (101 MHz, benzene-d6) δ 153.10, 136.65 (q, J = 29.6 Hz), 134.81 (dd, J = 2.7 Hz, 1.9 Hz), 133.93 (q, J = 3.6 Hz), 131.93 (q, J = 31.6 Hz), 131.35, 129.76 (q, J = 31.9 Hz), 127.26 (q, J = 274.6 Hz), 125.17 (d, J = 272.4 Hz), 124.89 (q, J = 272.8 Hz), 123.25 (q, J = 3.9 Hz), 119.89 (p, J = 3.9 Hz), 66.42, 64.08, 25.49, 24.57, 14.36. 1919F NMR (376 MHz, benzene-d6) δ -55.79, -62.66, -63.30. 11 11B NMR (160 MHz, benzene-d6) δ 5.32.

[0342] Preparation of Isopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane

[0343]

[0344] Trimethylchlorosilane (2.0 mL) was added to a solution of lithium diisopropoxy-(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate (3.318 g, 5.21 mmol) in diethyl ether (10 mL), and a precipitate formed rapidly. The reaction mixture was stirred overnight. The reaction mixture was filtered and the volatiles were removed under reduced pressure. NMR analysis showed completion of the reaction. There was also some putative TMS-O-iPr ether. A second batch of lithium diisopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate (2.017 g, 3.17 mmol, lithium salt; 2.0 mL TMSCl) prepared as described above was treated similarly and stirred for 3 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 first reaction product. All volatiles were removed under reduced pressure. The residue was extracted with hexane, filtered, and the volatiles were removed at 40 °C overnight under reduced pressure to give the product as a yellow oil, 3.4703 g, 83.42%.

[0345] 1 1H NMR (400 MHz, benzene-d6) δ 8.05 (d, J = 1.8 Hz, 2H), 7.80 (d, J = 2.3 Hz, 1H), 7.34 (d, J = 1.9 Hz, 1H), 7.12 (d, J = 6.5 Hz, 1H), 7.10 (d, J = 6.7 Hz, 1H), 3.78 (hept, J = 6.1 Hz, 1H), 0.85 (d, J = 6.1 Hz, 6H). 1313C NMR (101 MHz, benzene-d6) δ 139.07, 136.28, 135.37 (q, J = 31.8 Hz), 134.93 (d, J = 3.9 Hz), 133.49 (q, J = 32.7 Hz), 131.50 (q, J = 33.0 Hz), 127.87, 126.95 (dq, J = 7.5, 3.7 Hz), 126.46 (q, J = 3.7 Hz), 125.41 (hex, J = 3.8 Hz), 124.57 (q, J = 273.9 Hz), 123.98 (q, J = 272.8 Hz), 123.90 (q, J = 273.0 Hz), 72.49, 23.71. 19 19F NMR (376 MHz, benzene-d6) δ -60.31, -63.27 (d, J = 3.3 Hz), -63.47 (d, J = 3.3 Hz). 11 11B NMR (160 MHz, benzene-d6) δ 41.28.

[0346] Preparation of Lithium Isopropoxybis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borate

[0347]

[0348] n-Butyllithium (2.40 mL, 2.535 M in hexanes, 6.08 mmol) was slowly added to a cold (-78 °C, CO2(s) bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (1.800 g, 6.14 mmol) in diethyl ether (150 mL). The reaction mixture was stirred at -78 °C for 1 h. Isopropoxybis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borane (3.022 g, 6.09 mmol) in diethyl ether (18 mL) was slowly added. The reaction mixture was stirred at -78 °C for several hours. The solution was warmed to ambient temperature while stirring overnight to give a pale yellow clear solution. Volatiles were removed from the reaction mixture to give a yellow oil. The oil was extracted with benzene. There was no insoluble material. Volatiles were removed from the reaction mixture to give a yellow oil. The yield was 4.21 g, 87.6%.

[0349] 11H NMR (400 MHz, benzene-d6) δ 8.30 (s, 2H), 8.12 (s, 2H), 7.65 (dt, J = 1.7, 0.9 Hz, 1H), 7.27 (d, J = 8.2 Hz, 2H), 7.08 (d, J = 8.2 Hz, 2H), 3.87 (hept, J = 6.2 Hz, 1H), 2.91 (q, J = 7.1 Hz, 4H), 0.65 (d, J = 6.2 Hz, 6H), 0.63 (t, J = 7.1 Hz, 6H). 13 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 19F NMR (376 MHz, benzene-d6) δ -56.31, -62.89, -63.76. 11 11B NMR (160 MHz, benzene-d6) δ 2.98.

[0350] Preparation of bis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borane

[0351]

[0352] Trimethylchlorosilane (1.10 mL, 10.1 mmol) was added to a solution of lithium (diethyletherate)-isopropoxy-bis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borate (3.915 g, 4.95 mmol) in diethyl ether (150 mL) with stirring. A precipitate formed in the solution within 15 minutes. The reaction mixture was stirred overnight. The mixture was filtered and the volatiles were removed under reduced pressure to give a colorless solid, 3.260 g. The product was extracted with hexane, filtered, and the volatiles were removed under reduced pressure to give the product as a pale solid, 3.109 g, 96.53%.

[0353] 1 1H NMR (500 MHz, benzene-d6) δ 7.90 (s, 1H), 7.83 (s, 1H), 7.66 (s, 3H), 7.09 (s, 5H), 7.09 (s, 5H).13 C NMR (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.

[0354] The catalyst sample C7 was prepared as follows:

[0355] Preparation of tris(2,5-bis(trifluoromethyl)phenyl)borane

[0356]

[0357] This reaction was carried out in a manner similar to the previously reported procedure. 2 Isopropylmagnesium chloride-lithium chloride (46.0 mL, 58.0 mmol, 1.26 M in THF) was added to a solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (17.05 g, 58.2 mmol) in THF (250 mL), which was in an acetone bath cooled with dry ice (-76 °C). After the addition was complete, the reaction flask was transferred to an ice bath (0 °C) and the reaction mixture was stirred for 2 hours. The reaction mixture was cooled to -78 °C and boron trifluoride diethyl etherate (2.43 mL, 2.74 g, 19.3 mmol) in 15 mL of diethyl ether was added. The reaction mixture was allowed to warm to room temperature while stirring over the weekend. Volatiles were removed from the solution to give a slightly red solid, 12.77 g. The residue was extracted with toluene and filtered. Volatiles were removed under reduced pressure to give a pink powder, 10.75 g. The solid was extracted with dichloromethane to give a pale purple solution. The solution was placed in a freezer overnight. The supernatant was decanted from the very pale pink crystalline material that formed. The material was dried under reduced pressure overnight. Yield: 7.0003 g, 55.73%.

[0358] Product without TH: 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.

[0359] The catalyst sample C8, bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct, was prepared as follows:

[0360] Preparation of lithium isopropoxy(bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl))borate (tetrahydrofuran adduct)

[0361]

[0362]

[0363] Under stirring, n-butyllithium (3.00 mL, 2.54 M in hexanes, 7.61 mmol) was added to a cold (between -101 °C and -99 °C, CO2(s), then N2(l) methanol bath) solution of 1-bromo-2,3,5,6-tetrafluoro-4-trifluorotoluene (2.26 g, 7.61 mmol) in diethyl ether (100 mL). The reaction mixture was stirred at -100 °C for 2 h and then allowed to warm to -76 °C. Bis(3,5-bis(trifluoromethyl)phenyl)isopropoxy-borane (3.78 g, 7.61 mmol) in diethyl ether (10 mL) was slowly added to the reaction mixture. The reaction mixture was slowly warmed to ambient temperature while stirring overnight. The next day, the pale yellow almost clear solution was filtered and volatiles were removed from the filtrate under reduced pressure to give a crystalline solid. The solid was washed with hexanes, filtered and dried under reduced pressure. An aliquot of the solid was taken for NMR analysis. It had limited solubility in benzene. The aliquot was dissolved in THF and volatiles were removed under reduced pressure, and then analyzed by NMR again in benzene. Yield: 6.16 g, 93.2%.

[0364] 11H NMR (500 MHz, benzene-d6) δ 8.32 (s, 4H), 7.85 (s, 2H), 3.47 (h, J = 6.2 Hz, 1H), 3.26–3.17 (m, 4H), 1.24–1.16 (m, 4H), 0.55 (d, J = 6.2 Hz, 6H). 13 13C NMR (126 MHz, benzene-d6) δ 144.07 (d, J = 259.4 Hz), 134.41, 133.82, 133.48 (d, J = 187.5 Hz), 130.59 (q, J = 32.2 Hz), 130.45 (q, J = 31.8 Hz), 126.40–123.43 (m), 125.84, 124.97 (q, J = 272.4 Hz), 119.94 (p, J = 4.0 Hz), 118.92 (d, J = 190.9 Hz), 109.57 (d, J = 22.7 Hz), 68.38, 65.30, 25.64, 25.13. 19 19F NMR (470 MHz, benzene-d6) δ -56.26 (t, J = 20.7 Hz), -62.59, -137.04, -141.73. 11 11B NMR (160 MHz, benzene-d6) δ 1.20.

[0365] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane tetrahydrofuran adduct THF adduct

[0366]

[0367] Trimethylchlorosilane (2.00 mL, 18.4 mmol) was added to a solution of lithium isopropoxybis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)borate (6.16 g, 7.10 mmol) in diethyl ether (100 mL) with stirring. The reaction mixture was stirred overnight. The next day, 19 19F NMR spectroscopic analysis of an aliquot of the reaction mixture revealed that no reaction had occurred. A solution of hydrogen chloride in diethyl ether (7.00 mL, 2.0 M, 14.0 mmol) was added, and the reaction mixture was stirred overnight. The next day, 19Analysis of an aliquot of the reaction mixture by 19F NMR spectroscopy revealed completion of the reaction. The mixture was filtered and volatiles were removed from the filtrate under reduced pressure. The resulting residue was dissolved in toluene, filtered, and volatiles were removed from the filtrate under reduced pressure to give 4.50 g of the crude product. The colorless pasty solid was washed with hexane and filtered to give a colorless powder, which was dried under reduced pressure. NMR analysis of the powder revealed that one molecule of isopropanol remained in the coordination sphere of the borane. Yield of borane as the isopropanol adduct: 2.45 g, 52.8%.

[0368] A portion of the borane isopropanol adduct (1.811 g) was dissolved in diethyl ether (40 mL) and THF (10 mL) was added to the solution. The solution was allowed to evaporate slowly to give large crystals. The supernatant was removed and the very pale yellow crystals were washed with hexane. The crystals (1.08 g) were dried under reduced pressure. The crystals were analyzed by X-ray crystallography and found to be the borane isopropanol adduct. THF did not displace the coordinated alcohol. The supernatant solution and the hexane washings from the crystals were combined and concentrated in vacuo to give a second batch of crystals (0.422 g). The second batch of crystals was washed and dried in the same manner as the first batch. NMR analysis showed the presence of coordinated isopropanol but little or no THF. THF was added and then the volatiles were removed under reduced pressure. NMR analysis showed the presence of THF but still some isopropanol. The solid was dissolved in THF and then pumped out. This was repeated five more times to give the THF adduct as a white powder. Yield: 0.413 g, 22.4%.

[0369] THF adduct:

[0370] 1 1H NMR (400 MHz, benzene-d6) δ 7.87 (s, 4H), 7.80 (s, 4H), 3.02–2.93 (m, 4H), 0.78–0.72 (m, 4H). 13 13C NMR (126 MHz, benzene-d6) δ 147.98 (td, J = 16.5, 3.6 Hz), 146.05 (tt, J = 11.8, 4.1 Hz), 145.58 (d, J = 20.9 Hz), 143.50 (d, J = 20.1 Hz), 133.44, 131.39 (q, J = 32.6 Hz), 124.24 (q, J = 272.7 Hz), 121.78 (t, J = 4.0 Hz), 121.45 (q, J = 274.4 Hz), 109.38–108.10 (m), 73.75, 23.90. 1919F NMR (376 MHz, benzene-d6) δ -56.57 (t, J = 21.0 Hz), -62.95, -130.60 (dd, J = 22.5, 13.2 Hz), -140.71 (qt, J = 19.7, 8.6 Hz). 11 11B NMR (160 MHz, benzene-d6) δ 7.22.

[0371] The catalyst samples prepared as described above in Reference Example 2 are shown below.

[0372]

[0373] The structures of the fluorinated arylborane Lewis acid catalyst samples C1 - C8 and the commercially available FAB are shown above. Structure C1 is tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct (corresponding to starting material A1 in the claims). Structure C2 is bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct (corresponding to starting material A2 in the claims). Structure C3 is bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct (corresponding to starting material A3 in the claims). Structure C4 is bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct (corresponding to starting material A4 in the claims). Structure C5 is bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane (corresponding to starting material A5 in the claims). Structure C6 is (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane (corresponding to starting material A6 in the claims). 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 starting material A7 in the claims).

[0374] Reference Example 3 - General procedure

[0375] In a nitrogen-purged glove box, a 1 wt% catalyst solution was prepared in a glass vial by dissolving the solid catalyst sample shown above 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. The desired catalyst sample (e.g., 225 μL) was added via a micropipette to the stirred solution, followed by the slow addition of a silanol-terminated polydimethylsiloxane fluid (e.g., 8.4 g) over the course of 1 hour. An aliquot of the reaction mixture was removed, quenched with a drop of phenylacetylene and analyzed by 29 Si NMR in CDCl3 containing Cr(acac)3 as an NMR relaxant (∼1 g / 100 mL). The conversion was established by comparing the signals of HOSi(Me)2O-(MOH) with MeSiO3(T). The FAB 5 ppm runs (see Table 2) were carried out on a nitrogen-purged Schlenk line outside the glove box at batch scale (MH-1109 104.7 g, silanol-terminated polydimethylsiloxane fluid 80.1 g, FAB in toluene, 105 μL), delivering the silanol-terminated polydimethylsiloxane fluid over the course of 39 minutes using a peristaltic pump.

[0376] Example 4 - General procedure for stability monitoring

[0377] In a nitrogen-purged glove box, a 1 wt% solution of the above catalyst sample was prepared in a glass vial by dissolving the solid catalyst sample in anhydrous toluene. A cyclic polyorganohydrogensiloxane silane (MH-1109, 5 g) and a Teflon-coated stir bar were placed in the glass vial. The desired catalyst sample (e.g., 100.5 μL) was added via a micropipette to the stirred solution. Aliquots were sampled over time and quenched with a phenylacetylene / toluene mixture such that toluene could act as an internal standard. The aliquots were then analyzed by GC. The 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 carried out similarly outside the glove box using nitrogen-purged glass vials connected to the Schlenk line.

[0378] Dehydrogenative coupling reaction results

[0379] All of the tested triarylborane fluoride catalyst candidates (FAB, C1, C3, C5) showed some ability to catalyze the dehydrogenative coupling reaction shown below. However, side reactions (ring-opening polymerization / crosslinking) occurred when using FAB, which were monitored by the consumption of MH-1109 over time in the presence of the triarylborane fluoride Lewis acid catalyst. MH-1109 was monitored over time before the addition of the PA fluid. The stability study using only a 5 ppm loading of FAB gelled shortly after the 2-hour aliquot measurements. The study using a 100 ppm loading of FAB gelled almost immediately after the addition of the catalyst. All studies using one of samples C1, C3, or C5 did not gel for up to 24 hours after the addition of the catalyst and showed minimal signs of reaction with MH-1109, which was an unexpected result due to the similarity of the catalyst structures. This highly improved pot life is desirable for commercial-scale manufacturability.

[0380]

[0381] Dehydrogenative coupling model reaction. Note that the cyclic siloxane can have 4 - 6 siloxane units per molecule, and the corresponding cyclic groups in the product can each have 4 - 6 siloxane groups.

[0382] Table 2. Conversion data for dehydrogenative coupling between MH-1109 and silanol fluids with various catalysts 。

[0383] Catalyst Catalyst loading (ppm) Time (h) Conversion FAB 100 -* -* FAB 5 1 >99％ C1 100 1.5 12％ C1 100 19 17％ C3 100 1.5 6％ C3 100 19 7％ C5 100 1.3 99％ C5 100 18.7 98％

[0384] * Indicates that the reaction gelled (<2 minutes) before the addition of the silanol fluid.

[0385] Definition and usage of terms

[0386] The abbreviations used in the specification have the definitions in Table 5 below.

[0387] Table 5 - Abbreviations

[0388]

[0389]

[0390] Unless otherwise indicated, all amounts, ratios, and percentages are by weight. The amounts of all starting materials in the composition total 100% by weight. The Summary of the Invention and the Abstract of the Specification are hereby incorporated by reference. Unless the context of this specification indicates otherwise, each of the articles "a", "an", and "the" refers to one or more. The singular includes the plural meaning unless otherwise indicated. The disclosure of a range includes the range itself and any values and endpoints contained therein. For example, the disclosure of the range 2.0 to 4.0 includes not only the range 2.0 to 4.0, but also individually 2.1, 2.3, 3.4, 3.5, and 4.0 and any other numbers contained in that range. In addition, for example, the disclosure of the range 2.0 to 4.0 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 and any other subsets contained in that range. Similarly, the disclosure of a Markush group includes the entire group and also includes any individual members and subgroups contained therein. For example, the disclosure of the Markush group hydrogen atom, alkyl group, alkenyl group, or aryl group includes the individual member alkyl; the alkyl and aryl subgroups; and any other individual members and subgroups contained therein.

[0391] The term "comprising" and its derivatives, such as "having" and "containing", are used in their broadest sense herein, meaning and encompassing the concepts of "including", "consisting essentially of", and "consisting of". The use of "for example", "for instance", "such as", and "including" to list exemplary examples does not mean limited to 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.

[0392] Generally speaking, as used herein, the hyphen "-" or dash "–" within a range of values is "to" or "until"; ">" is "higher than" or "greater than"; "≥" is "at least" or "greater than or equal to"; "<" is "lower than" or "less than"; and "≤" is "at most" or "less than or equal to". Each of the foregoing patent applications, patents, and / or patent application publications is hereby incorporated by reference in its entirety in one or more non-limiting embodiments.

[0393] It should be understood that the appended claims are not limited to the specific compounds, compositions, or methods described in the specific embodiments, which may vary between specific embodiments falling within the scope of the appended claims.

Claims

1. A method for preparing a product comprising a polyfunctional organohydrogensiloxane, wherein the method comprises: 1) Combining starting materials comprising the following Formula (A) triarylborane fluoride Lewis acid; wherein 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 each independently selected from H, F or CF3; R 2 comprises a functional group; and the subscript x is 0 or 1; provided that: Not all Rs o1 、Rs o2 、Rs o3 、Rs o4 、Rs o5 、Rs o6 、Rs m1 、Rs m2 、Rs m3 、Rs m4 、Rs m5 、Rs m6 、Rs p1 、Rs p2 and Rs p3 can all be F simultaneously; Not all of R o1-6 , R m1-6 and R p1-3 can be H simultaneously; R m1 , R m2 and R m3 Each of is CF3; and When R o1 、R o2 、R o3 and R o4 are CF3, then R o5 and R o6 are each independently selected from H or F; B) formula hydroxy-functionalized organosilicon compound, where the subscript n is from 1 to 2,000, and each R 1 is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group; and C) cyclic polyorganohydrogensiloxanes of the formula (RHSiO 2 / 2 ) v wherein the subscript v is from 3 to 12 and each R is an independently selected monovalent hydrocarbon radical; thereby producing a product containing a polyfunctional organohydrogensiloxane and a by-product containing H2.

2. The method according to 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 method according to claim 1, wherein the hydroxy-functionalized organosilicon compound B) comprises a hydroxy-terminated polydiorganosiloxane, the subscript n is from 2 to 1,000, and each R 1 is 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 haloalkyl groups having 1 to 20 carbon atoms.

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

5. The method according to claim 1 further comprises: 2) During and / or after step 1), removing H2 generated during the formation of the polyfunctional organohydrogensiloxane.

6. The method according to claim 1 further comprises: 3) Neutralizing the residual fluorinated triarylborane Lewis acid in the polyfunctional organohydrogensiloxane.

7. The method according to claim 6, wherein the polyfunctional organohydrogensiloxane has the general formula a-1): wherein each subscript v is independently from 3 to 12; each subscript n is independently from 1 to 1,000; each R is an independently selected monovalent hydrocarbon group; and each R 1 is independently selected from a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, provided that one or more hydrogen atoms in formula (a-1) are replaced by a group of formula (a-2): wherein each of the subscript n, subscript v, R, and R 1 is independently selected and as described above.

8. The method according to claim 6, wherein the polyfunctional organohydrogensiloxane has the following formula: where each subscript v is independently from 3 to 12; each subscript n is independently from 1 to 1,000; each R is an independently selected monovalent hydrocarbon group; and each R 1 is independently selected from a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group.

9. The method according to claim 1, further comprising recovering the polyfunctional organohydrogensiloxane from the product.

10. A method for preparing a clustered functionalized organopolysiloxane, the method comprising: 1) Preparing a) a product by the method according to any one of claims 1 to 3 and 5 to 9, and 2) Combining starting materials comprising the following a) the product, b) a hydrosilylation reaction catalyst, and c) a reactive substance having on average at least one aliphatic unsaturated group per molecule, the at least one aliphatic unsaturated group being capable of undergoing an addition reaction with the silicon-bonded hydrogen atoms of starting material a), and each molecule further comprising one or more curable groups.

11. The method according to claim 10, wherein the reactive substance is selected from the group consisting of: i) A silane of the formula R 4 y SiR 5 (4-y) where the subscript y is from 1 to 3, each R 4 is an aliphatic unsaturated group capable of undergoing an addition reaction, and each R 5 is the curable group; thereby preparing a product comprising a clustered functionalized organosiloxane; and ii) An organic compound of formula R 6 R 7 wherein each R 6 is an aliphatic unsaturated group capable of undergoing an addition reaction, and each R 7 is said curable group.

12. The method according to claim 10, wherein the clustered functionalized organopolysiloxane has the general formula a'-1): where each subscript v is independently from 3 to 12; each subscript n is independently from 1 to 1,000; each R is an independently selected monovalent hydrocarbon group; each R 1 is independently selected from a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group; and where each R 8 is independently selected from the group consisting of H and a curable group, provided that one or more of the Rs 8 is replaced by a group of formula a'-2): wherein subscript n, subscript v, R, R 1 and R 8 are as described above; provided that at least one R per molecule 8 is the curable group.

13. The method according to claim 12, wherein the clustered functionalized organopolysiloxane has the following formula: where each subscript v is independently from 3 to 12; each subscript n is independently from 1 to 1,000; each R is an independently selected monovalent hydrocarbon group; each R 1 is independently selected from a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group; and where each R 8 is independently selected from the group consisting of H and a curable group.

14. A curable composition, the 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. A composition, the composition comprising: Formula (A) triarylborane fluoride Lewis acid; wherein 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 each independently selected from H, F or CF3; R 2 comprises a functional group; and the subscript x is 0 or 1; provided that: Not all of 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 can all be F simultaneously; Not all of R o1-6 , R m1-6 and R p1-3 can be H simultaneously; R m1 , R m2 and R m3 Each of is CF3; and When R o1 , R o2 , R o3 and R o4 are such that two or more of them are CF3, then R o5 and R o6 are each independently selected from H or F; B) formula hydroxy-functionalized organosilicon compound, where the subscript n is from 1 to 2,000, and each R 1 is independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups; and C) cyclic polyorganohydrogensiloxanes of the formula (RHSiO 2 / 2 ) v wherein the subscript v is from 3 to 12 and each R is an independently selected monovalent hydrocarbon radical; thereby producing a product comprising a polyfunctional organohydrogensiloxane and a by-product comprising H2.

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