Catalysts, redox-switch catalyst systems, and related processes involving hydrosilylation

Abstract

A hydrosilylation catalyst is disclosed. The catalyst includes a complex having a specific formula. A redox switch catalyst system for preparing the catalyst is also disclosed. The redox switch catalyst system includes a redox switch catalyst and a reducing compound. The reducing compound reduces the formal oxidation state of the redox switch catalyst to obtain a catalyst, the former being generally inactive in catalyzing hydrosilylation and the latter being catalytically active. A composition including the catalyst and / or redox switch catalyst system and a hydrosilylation reaction product is also disclosed.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and all benefits of U.S. Provisional Patent Application No. 63 / 048,613, filed July 6, 2020, the contents of which are incorporated herein by reference.

[0002] The present invention relates generally to catalysts, more specifically to hydrosilylation catalysts and redox-switch catalyst systems for preparing the catalysts. The present invention also relates to compositions comprising the same and related methods. [Background technology]

[0003] Hydrosilylation reactions are generally known in the art and involve the addition reaction between silicon-bonded hydrogen and aliphatic unsaturation.Hydrosilylation reactions are utilized in a variety of applications.For example, curable compositions often rely on hydrosilylation reactions to cure or crosslink their components to obtain cured products.Hydrosilylation reactions can also be utilized to prepare individual components or compounds, such as components for inclusion in curable compositions.

[0004] The hydrosilylation reaction is typically carried out in the presence of a platinum metal catalyst due to its excellent catalytic activity. Metal complexes can also be used to catalyze the hydrosilylation reaction. However, it is difficult to control the catalytic activity of the catalyst, which affects the timing of the initiation of the hydrosilylation reaction. Summary of the Invention

[0005] The present invention provides a hydroxylation catalyst having the following formula: [ka] , wherein each R is an independently selected hydrocarbyl group; 1are independently selected aryl groups and X is a halogen atom.

[0006] The present invention also provides a redox-switch catalyst system for preparing a catalyst, the redox-switch catalyst system having the following formula: [ka] wherein each R is independently selected and defined above; and each R 1 are independently selected and defined above, each X is independently a halogen atom, and A is a counteranion. The redox switch catalyst system further comprises a reducing compound. The present invention also provides a method for preparing a catalyst using the redox switch catalyst system. The method comprises reducing the redox switch catalyst with a reducing compound to obtain the catalyst.

[0007] The present invention also provides a method for preparing a catalyst, the method comprising: 2 2X]2 starting material (I) and [ka] The catalyst is obtained by complexing the starting material (I) with the starting material (II) of 2 are independently selected aliphatic unsaturated groups, and each X is an independently selected halogen atom. In starting material (II), R is a hydrocarbyl group, and each R 1 is an independently selected aryl group.

[0008] The present invention also provides a composition comprising (A) an unsaturated compound containing at least one aliphatic unsaturated group per molecule, subject to at least one of the following two conditions: (1) the (A) unsaturated compound also contains at least one silicon-bonded hydrogen atom per molecule, and / or (2) the composition further comprises (B) a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule. The composition further comprises a catalyst and / or a redox-switch catalyst system.

[0009] Also provided is a method for preparing a hydrosilylation reaction product. The method comprises reacting an aliphatically unsaturated group and a silicon-bonded hydrogen atom in the presence of a catalyst to obtain a hydrosilylation reaction product. The aliphatically unsaturated group is present in (A) an unsaturated compound, subject to the same conditions as described above for the composition. The catalyst may be formed in situ in the method from a redox-switch catalyst system. [Brief explanation of the drawings]

[0010] Other advantages of the present invention will be readily appreciated as the same becomes better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings.

[0011] [Figure 1] 1 shows the storage modulus, loss modulus, and temperature as a function of time associated with the curing process monitored in real time by the rheometer of Example 6. [Figure 2] 1 shows the storage modulus, loss modulus, and temperature as a function of time associated with the curing process monitored in real time by the rheometer of Example 7. [Figure 3] 1 shows the storage modulus, loss modulus, and temperature as a function of time associated with the curing process monitored in real time by the rheometer of Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention provides a catalyst that has excellent physical properties and catalytic activity in hydrosilylation reactions. The catalyst can be formed in situ from a redox-switching catalyst system, thereby enabling selective control or initiation of hydrosilylation based on such redox switching (i.e., converting to "on" via a formal change in oxidation state).

[0013] The catalyst has the following structure: [ka] , wherein each R is an independently selected hydrocarbyl group; 1 are independently selected aryl groups, and X is a halogen atom.

[0014] The halogen atom represented by X can be fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), or tennessine (T). In certain embodiments, X is Br or Cl. In certain embodiments, X is Cl.

[0015] Each R is independently selected and may be linear, branched, cyclic, or a combination thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may be monocyclic or polycyclic. Linear and branched hydrocarbyl groups may independently be saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. "Substituted" means that one or more hydrogen atoms may be replaced with atoms other than hydrogen (e.g., halogen atoms such as chlorine, fluorine, bromine, etc.), or that a carbon atom in the chain of R may be replaced with an atom other than carbon, i.e., R may contain one or more heteroatoms in the chain, such as oxygen, sulfur, nitrogen, etc. Typically, each R does not contain heteroatoms. Suitable alkyl groups are exemplified by, but not limited to, methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl and / or tert-pentyl), hexyl, and branched saturated hydrocarbon groups of 6 carbon atoms. Suitable aryl groups are exemplified by, but not limited to, phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl groups. Suitable monovalent halogenated hydrocarbon groups include, but are not limited to, halogenated alkyl groups having 1 to 6 carbon atoms or halogenated aryl groups having 6 to 10 carbon atoms. Suitable halogenated alkyl groups are exemplified, but not limited to, by the alkyl groups described above in which one or more hydrogen atoms have been replaced with a halogen atom such as F or Cl.For example, fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl are examples of suitable halogenated alkyl groups.Suitable halogenated aryl groups are exemplified by, but not limited to, the above-mentioned aryl groups in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl.For example, chlorobenzyl and fluorobenzyl are suitable halogenated aryl groups.

[0016] In certain embodiments, each R is an independently selected alkyl group, which may be linear, branched, cyclic (e.g., cycloalkyl), or a combination thereof. In certain embodiments, each R is linear or branched. In certain embodiments, each R is linear.

[0017] Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, hexadecyl, and octadecyl, as well as branched saturated hydrocarbon groups having 6 to 8 carbon atoms. Examples of suitable non-conjugated cyclic groups (i.e., cycloalkyl groups) include cyclobutyl, cyclohexyl, and cycloheptyl groups.

[0018] In certain embodiments, each R independently has 1 to 8, alternatively 1 to 7, alternatively 1 to 6, alternatively 1 to 5, alternatively 1 to 4, alternatively 1 to 3, alternatively 1 to 2, or alternatively 1 carbon atom.

[0019] Each R 1 may also be independently selected hydrocarbyl groups. Typically, however, each R 1 are independently selected aryl groups. Aryl groups have at least 5 carbon atoms. Aryl groups can be monocyclic or polycyclic. Monocyclic aryl groups can have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, alternatively 6 carbon atoms. Polycyclic aryl groups can have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, alternatively 12 to 14 carbon atoms. Aryl is exemplified by, but not limited to, phenyl and naphthyl. In certain embodiments, each R 1 is a monocyclic aryl group. In certain embodiments, each R 1 is a phenyl group.

[0020] In certain embodiments, each R and each R 1 R and R are independently selected based on factors such as steric hindrance, electronic properties (e.g., electron donating, inductive, or withdrawing effects), or a combination thereof. 1 may be selected to impart symmetry to the catalyst. In these or other embodiments, R and R 1 can be independently selected to impart reactive regioselectivity.

[0021] An exemplary embodiment of the catalyst is shown below: 1 is phenyl and X is Cl]: [ka] [Ph represents phenyl].

[0022] The catalyst can be in or on a solid support, examples of which include activated carbon, silica, silica alumina, alumina, zeolites, and other inorganic powders / particles (e.g., sodium sulfate).

[0023] The catalyst may also be placed in a vehicle, such as a solvent that solubilizes the catalyst, or a vehicle that simply supports or disperses but does not solubilize the catalyst. Such vehicles are known in the art.

[0024] Suitable vehicles include both linear and cyclic silicones, organic oils, organic solvents, and mixtures thereof. For example, for silicones, the carrier vehicle can include polydialkylsiloxanes, such as polydimethylsiloxanes.

[0025] The vehicle may also be a siloxane having a viscosity of 1 to 1,000 mm at 25° C., such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadeamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy}trisiloxane, hexamethyl-3,3,bis{(trimethylsilyl)oxy}trisiloxanepentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, as well as polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, and any mixture thereof. 2 The organopolysiloxane may be a low viscosity organopolysiloxane, or a volatile methyl siloxane, or a volatile ethyl siloxane, or a volatile methylethyl siloxane, having a viscosity in the range of 1 / sec.

[0026] Alternatively, the vehicle may comprise an organic solvent. Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, etc.; aliphatic hydrocarbons such as heptane, hexane, octane, etc.; glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether, etc.; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, and chloroform; ketones such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, acetates such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, and propylene glycol methyl ether acetate, etc.; alcohols such as methanol, ethanol, isopropanol, butanol, or n-propanol; and other organic compounds that exist as liquids / fluids at typical reaction temperatures, such as dimethyl sulfoxide, dimethylformamide, acetonitrile, tetrahydrofuran, white spirit, mineral spirits, naphtha, n-methylpyrrolidone, etc., as well as derivatives, modifications, and combinations thereof.

[0027] The catalyst may also be in a crystalline state, e.g., grown from a supersaturated solution in a vehicle, but the catalyst is typically homogeneous, not heterogeneous, to maximize contact interaction with the components of the catalyst in the hydrosilylation reaction.

[0028] The present invention also provides a method for preparing a catalyst, the method comprising: 2 2X]2 starting material (I) and [ka] The catalyst is obtained by complexing the starting material (I) with the starting material (II) of 2 is an independently selected aliphatic unsaturated group, and X is an independently selected halogen atom. In starting material (II), R is a hydrocarbyl group, and each R 1is an independently selected aryl group.

[0029] In this method of preparing the catalyst, the catalyst is prepared directly. However, as described in more detail below, the catalyst can also be prepared from a redox-switch catalyst system. The use of a catalyst prepared directly or via a redox-switch catalyst system is a function of the desired end use related to hydrosilylation. For example, the prepared catalyst can be used to replace any conventional hydrosilylation catalyst, typically based on platinum. However, when the catalyst is prepared from a redox-switch catalyst system, the catalyst can be formed in situ, for example, in the presence of the reactants of the hydrosilylation-curable composition. This allows for selective control of the onset of hydrosilylation, rather than initiation, based on the combination of reactants, as described in more detail below.

[0030] The starting material (I) is a compound of the formula [RhR 2 2X]2. Each X is independently selected, and suitable examples are described above with reference to the catalyst. Typically, each X is Br or Cl, or Cl. Each R 2are independently selected aliphatically unsaturated groups, which are independently selected alkenyl and / or alkyl groups having 2 to 12, alternatively 2 to 11, alternatively 2 to 10, alternatively 2 to 9, alternatively 2 to 8, alternatively 2 to 7, alternatively 2 to 6, alternatively 2 to 5, alternatively 2 to 4, alternatively 2 to 3, or alternatively 2 carbon atoms. "Alkenyl" refers to an acyclic, branched, or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. Specific examples include vinyl, allyl, and hexenyl. "Alkynyl" refers to an acyclic, branched, or unbranched monovalent hydrocarbon group having one or more carbon-carbon triple bonds. Specific examples include ethynyl, propynyl, and butynyl. Various examples of ethylenically unsaturated groups include CH2=CH-, CH2=CHCH2-, CH2=CH(CH2)4-, CH2=CH(CH2)6-, CH2=C(CH3)CH2-, HC=C(CH3)-, HC=C(CH3)-, HC=C(CH3)CH2-, HC=CHCH2CH2-, HC=CHCH2CH2CH2-, HC≡C-, HC≡CCH2-, HC≡CCH(CH3)-, HC≡CC(CH3)2-, and HC≡CC(CH3)2CH2-. Typically, aliphatic unsaturation occurs within the R 2 As is understood in the art, aliphatic unsaturation is sometimes referred to as ethylenic unsaturation. In certain embodiments, each R 2 is vinyl.

[0031] A specific example of starting material (I) is chlorobis(ethylene)rhodium dimer, having the formula RhCl(CH) or alternatively written as [Rh(CH)Cl]. This starting material (I) contains two bridging chloride ligands and four ethylene ligands and has the following structure: [ka] It has.

[0032] Starting material (II) is R of starting material (I). 2By substitution, it complexes with the starting material (I) as a ligand.

[0033] R and R of starting material (II) 1 Specific examples of R and R of starting material (II) 1 However, upon ligand formation, R and R of the catalyst 1 and is therefore defined above with reference to the catalyst.

[0034] Illustrative examples of starting material (II) include those having the structure: [ka] The compound is 2-(diphenylphosphino)anisole, having the formula:

[0035] Typically, the catalyst is formed from starting material (II) and starting material (I) in a molar ratio of starting material (II) to starting material (I) of 4:1. However, a molar or stoichiometric excess of starting material (I) or starting material (II) can be utilized relative to the other. The reaction for complexing starting material (II) with starting material (I) can be carried out in a support, examples of which are described above. The reaction can be carried out under ambient conditions, but can optionally be carried out in an inert atmosphere (e.g., nitrogen) while controlling or modifying temperature, humidity, pressure, etc. from ambient conditions.

[0036] As noted above, a redox-switch catalyst system for preparing a catalyst is also provided. The redox-switch catalyst system has the following formula: [ka] wherein each R is independently selected and defined above; and each R 1 are independently selected and defined above, each X is independently selected and defined above, and A is a counter anion.

[0037] In certain embodiments, the counteranion A has the formula (BQ4): -wherein B is boron in a formal oxidation state of 3, and each Q is independently selected from a hydrocarbyl group, a hydrocarbyloxy group, a fluorinated hydrocarbyl group, a fluorinated hydrocarbyloxy group, or a fluorinated silylhydrocarbyl group, provided that no more than one Q is hydrocarbyl. Most typically, each Q is selected from a fluorinated aryl group, such as a pentafluorophenyl or nonafluorobiphenyl group. Specific examples of such counter anions include tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tetrakis[pentafluorophenyl]borate, and tetrakis(nonafluorobiphenyl)borate. Alternatively, the counter anion A can include hexafluorophosphate, tetrafluoroborate, and / or aluminum perfluoroalkoxide. Furthermore, the counter anion A can include a halide.

[0038] Generally, unlike the catalysts described above, the redox switch catalyst of the redox switch catalyst system is not active in catalyzing hydrosilylation. However, via reduction with a reducing compound, the redox switch catalyst can be converted to a catalyst that is catalytically active for hydrosilylation.

[0039] The redox switch catalyst system further comprises such a reducing compound. In certain embodiments, the reducing compound serves to reduce the formal oxidation state of the rhodium atom in the redox switch catalyst, resulting in the catalyst. Examples of reducing compounds include alkali metal amalgams; hydrogen; metal hydrides such as lithium aluminum hydride (LiAlH), diisobutylaluminum hydride, or sodium naphthalenide; silyl hydrides; or metal borohydrides such as sodium triethylborohydride (NaEtBH), lithium triethylborohydride (LiEtBH), or sodium borohydride (NaBH). In certain embodiments, the liquid composition of claim 1 comprises: (i) a borohydride compound; (ii) an aluminum hydride compound; (iii) an organolithium compound; (iv) an organomagnesium compound; or (v) any combination of (i)-(iv). In certain embodiments, the reducing compound comprises bis(cyclopentadienyl)cobalt(II) or cobaltocene. Additional examples of suitable reducing compounds include zinc dust or particles, trichlorotris(tetrahydrofuran)titanium(III), and / or hydrazine. Another specific example of a reducing compound is tetrakis(dimethylamino)ethylene (TDAE).

[0040] The present invention further provides a method for preparing a catalyst using a redox switch catalyst, the method comprising reducing the redox switch catalyst with a reducing compound, the redox switch catalyst and the reducing compound being described above.

[0041] The present method allows for selective control of the initiation of hydrosilylation in a hydrosilylation-curable composition. For example, when forming a conventional hydrosilylation-curable composition containing a conventional hydrosilylation catalyst, hydrosilylation is typically initiated, even if only partially, at ambient conditions. However, because redox-switch catalysts are typically inactive in catalyzing hydrosilylation, the redox-switch catalyst can be placed in the hydrosilylation-curable composition without initiating hydrosilylation or at a particularly low conversion rate to prevent gelation. The redox-switch catalyst can be reduced via a reducing compound at any desired time by combining the hydrosilylation-curable composition containing the redox-switch catalyst with a reducing compound, at which point the redox-switch catalyst is converted to a catalyst via a formal change in its oxidation state and becomes catalytically active (for hydrosilylation). The redox-switch catalyst can be reduced with a reducing compound to obtain the catalyst before incorporating the catalyst into the hydrosilylation-curable composition, or it can be reduced in situ so that the catalyst is formed in situ.

[0042] The relative amounts of catalyst and reducing compound can vary in both the redox-switch catalyst system and the associated method of reducing the redox-switch catalyst, depending, for example, on the selection of catalyst, reducing compound, ligand, etc. Those skilled in the art will readily understand how to determine appropriate molar ratios given these choices.

[0043] The redox switch catalyst system typically forms a reaction product when a reducing compound reductively converts the redox switch catalyst to a catalyst. Catalytic reaction products formed from the redox switch catalyst system are also provided. The catalytic reaction product is typically used when catalyzing hydrosilylation and, as described above, can be formed prior to or simultaneously with catalyzing the reaction (e.g., the catalytic reaction product is formed in situ). The catalytic reaction product includes the catalyst.

[0044] As introduced above, the present invention also provides a composition. The composition includes an (A) unsaturated compound. The (A) unsaturated compound includes at least one aliphatic unsaturated group per molecule, which may alternatively be referred to as ethylenically unsaturated. The (A) unsaturated compound is not limited and may be any unsaturated compound having at least one aliphatic unsaturated group. In certain embodiments, the (A) unsaturated compound includes an organic compound. In other embodiments, the (A) unsaturated compound includes a siloxane. In yet other embodiments, the (A) unsaturated compound includes a silicone-organic hybrid or an organosilicon compound. Various embodiments and examples of the (A) unsaturated compound are disclosed below.

[0045] In certain embodiments, the (A) unsaturated compound contains an average of at least two aliphatic unsaturated groups per molecule. In such embodiments, the (A) unsaturated compound is capable of polymerization or curing beyond single cure-site hydrosilylation. The aliphatic unsaturated groups of the (A) unsaturated compound can be at terminal, pendant, or both positions on the (A) unsaturated compound.

[0046] For example, the aliphatic unsaturated group can be an alkenyl group and / or an alkynyl group. An "alkenyl group" refers to an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. An alkenyl group can have 2 to 30 carbon atoms, alternatively 2 to 24 carbon atoms, alternatively 2 to 20 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, or alternatively 2 to 6 carbon atoms. Alkenyl groups are exemplified, but not limited to, by vinyl, allyl, propenyl, and hexenyl. An "alkynyl group" refers to an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon triple bonds. An alkynyl group can have 2 to 30 carbon atoms, alternatively 2 to 24 carbon atoms, alternatively 2 to 20 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, or alternatively 2 to 6 carbon atoms. Alkynyl is exemplified, but not limited to, by ethynyl, propynyl, and butynyl.

[0047] In certain embodiments, the (A) unsaturated compound has the formula R 2 -ZR 2 where Z is a divalent linking group which may be a divalent hydrocarbon, polyoxyalkylene, polyalkylene, polyisoalkylene, hydrocarbon-silicone copolymer, siloxane, or mixtures thereof (block or randomized). Z may be linear or branched. In certain of these embodiments, R 2 are independently selected and contain aliphatic unsaturation, i.e., each R 2 is independently selected from alkenyl and alkynyl groups.

[0048] In certain of these embodiments, (A) the unsaturated compound is R 2 It contains two aliphatic unsaturated groups represented by the formula:

[0049] In one embodiment of the (A) unsaturated compound, Z is a divalent hydrocarbon. The divalent hydrocarbon Z may contain 1 to 30 carbons, either as an aliphatic or aromatic structure, and may be branched or unbranched. Alternatively, the linking group Z may be an alkylene group containing 1 to 12 carbons. In these embodiments, the (A) unsaturated compound may be selected from α,ω-unsaturated hydrocarbons. Alternatively, the α,ω-unsaturated hydrocarbons may be referred to as olefins.

[0050] For example, (A) the unsaturated compound can be any diene, diyne, or enyne compound. Referring to the formula above, in these embodiments, R 2 may be, for example, independently selected from CH2=CH-, CH2=CHCH2-, CH2=CH(CH2)4-, CH2=C(CH3)CH2-, or similarly substituted unsaturated groups such as HC=C(CH3)-, and HC=C(CH3)-. In such embodiments, (A) the unsaturated compound may be referred to as an α,ω-unsaturated hydrocarbon. An α,ω-unsaturated hydrocarbon may be, for example, a compound of the formula CH2=CH(CH2) b α,ω-dienes of CH=CH2, formula CH≡C(CH2) b α,ω-diynes with C≡CH, formula CH2=CH(CH2)b C≡CH α,ω-ene-ynes, or mixtures thereof, where b is independently 0-20, alternatively 1-20.

[0051] Specific examples of suitable diene, diyne or ene-yne ​​compounds include 1,4-pentadiene, 1,5-hexadiene; 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene, and 1,19-eicosadiene, 1,3-butadiyne, 1,5-hexadiyne (dipropargyl), and 1-hexen-5-yne.

[0052] However, (A) the unsaturated compound may alternatively be of formula R 2 -Z', where R 2 is defined above, and Z' is a monovalent hydrocarbon group (or a silyl or siloxane group). In certain of these embodiments, (A) the unsaturated compound is R 2 It contains one aliphatic unsaturated group represented by:

[0053] When the (A) unsaturated compound contains only one aliphatic unsaturated group, the (A) unsaturated compound may be referred to as an unsaturated hydrocarbon and may be any -ene or -yne compound. In such embodiments, the (A) unsaturated compound may be an acyclic alkene and / or an acyclic alkyne. However, the (A) unsaturated compound may contain an aryl group, so long as it also contains at least one aliphatic unsaturated group independent of any aryl group, e.g., pendant independent of any aryl group.

[0054] In other embodiments, the (A) unsaturated compound comprises or is a polyether. In these embodiments, the (A) unsaturated compound has the formula (C a H 2a O), where a is 2 to 4. Referring to the general formula above, Z' is a polyoxyalkylene group. In these embodiments, the (A) unsaturated compound may be referred to as a polyoxyalkylene.

[0055] The polyoxyalkylene may contain oxyethylene units (C2H4O), oxypropylene units (C3H6O), oxybutylene or oxytetramethylene units (C4H8O), or mixtures thereof, which may be in block form or randomized in the (A) unsaturated compound.

[0056] For example, the unsaturated compound (A) as a polyoxyalkylene may be represented by the following general formula: R 2 O-[(C2H4O) c (C3H6O) d (C4H8O) e ]-R 2 [In the formula, each R 2 are independently selected and defined above, c is 0 to 200, d is 0 to 200, and e is 0 to 200, provided that c, d, and e are not simultaneously 0. In certain embodiments, c is 0 to 50, alternatively 0 to 10, alternatively 0 to 2. In these or other embodiments, d is 0 to 100, alternatively 1 to 100, alternatively 5 to 50. In these or other embodiments, e is 0 to 100, alternatively 0 to 50, alternatively 0 to 30. In various embodiments, the ratio of (d+e) / (c+d+e) is greater than 0.5, alternatively 0.8, alternatively 0.95.

[0057] The polyoxyalkylene may have independently selected R groups, as described above, at each chain end (i.e., alpha and omega positions). 2 It is terminated with R 2 Further examples include H2C=C(CH3)CH2-H2C=CHCH2CH2-, H2C=CHCH2CH2CH2-, and H2C=CHCH2CH2CH2CH2-, HC≡C-, HC≡CCH2-, HC≡CCH(CH3)-, HC≡CC(CH3)2-, and HC≡CC(CH3)2CH2-. However, the above polyoxyalkylenes are merely examples of suitable polyoxyalkylenes.

[0058] In certain embodiments, the polyoxyalkylene group contains only oxypropylene units (CHO). Representative, non-limiting examples of polyoxypropylene-containing polyoxyalkylenes include HC=CHCH[CHO] d CH2CH=CH2, H2C=CH[C3H6O] d CH=CH2, H2C=C(CH3)CH2[C3H6O] d CH2C(CH3)=CH2, HC≡CCH2[C3H6O] d CH2C=CH, and HC≡CC(CH3)2[C3H6O] d C(CH3)2C≡CH, where d is as defined above.

[0059] Representative, non-limiting examples of polyoxyalkylene-containing polyoxybutylene or poly(oxytetramethylene) include H2C=CHCH2[C4H8O] e CH2CH=CH2, H2C=CH[C4H8O] e CH=CH2, H2C=C(CH3)CH2[C4H8O] e CH2C(CH3)=CH2, HC≡CCH2[C4H8O] e CH2C≡CH, and HC≡CC(CH3)2[C4H8O] e C(CH3)2C≡CH, where e is as defined above.

[0060] Examples of polyoxyalkylenes suitable for the (A) unsaturated compound include two aliphatic unsaturated groups. However, polyoxyalkylenes suitable for the (A) unsaturated compound may contain only one aliphatic unsaturated group. For example, polyoxyalkylenes suitable for the (A) unsaturated compound may alternatively be represented by the following general formula: R 2 O-[(C2H4O) c (C3H6O) d (C4H8O) e ]-R 3 [In the formula, R 2 , c, d, and e are defined above, and R 3is an alkyl group such as H or CH. Any of the above descriptions or examples also apply to this embodiment. Those skilled in the art will readily understand how the above polyoxyalkylene example having two aliphatic unsaturated groups can alternatively contain only one aliphatic unsaturated group.

[0061] Polyoxyalkylenes can be prepared, for example, by polymerization of ethylene oxide, propylene oxide, butylene oxide, 1,2-epoxyhexane, 1,2-epoxyoctane, and / or cyclic epoxides such as cyclohexene oxide or exo-2,3-epoxynorborane. The polyoxyalkylene portion of the polyoxyalkylene can contain oxyethylene units (C2H4O), oxypropylene units (C3H6O), oxybutylene units (C4H8O), or mixtures thereof. Typically, polyoxyalkylene groups are defined on a molar basis and contain a majority of oxypropylene or oxybutylene units, as indicated by the subscripts c, d, and e in the formula above.

[0062] In another embodiment, the general formula R 2 -ZR 2 or (A) an unsaturated compound of formula R 2 Z' in -Z' comprises a polyalkylene group. The polyalkylene group may contain C2 to C6 alkylene units or isomers thereof. One specific example is a polyisobutylene group, which is a polymer containing isobutylene units. For example, the (A) unsaturated compound may be diallyl-terminated polyisobutylene or allyl-terminated polyisobutylene. The molecular weight of the polyisobutylene group may vary, but is typically in the range of 100 to 10,000 g / mol.

[0063] In certain embodiments, (A) the unsaturated compound comprises an organopolysiloxane. The organopolysiloxane is not limited and can be any organopolysiloxane containing at least one silicon-bonded aliphatic unsaturated group per molecule. For example, the organopolysiloxane can be linear, branched, partially branched, cyclic, resinous (i.e., having a three-dimensional network), or can include a combination of different structures. When (A) the unsaturated compound comprises an organopolysiloxane, the aliphatic unsaturated group is silicon-bonded (e.g., as a silicon-bonded alkenyl and / or silicon-bonded alkynyl).

[0064] In certain embodiments, when (A) the unsaturated compound comprises an organopolysiloxane, the organopolysiloxane has the following average formula: R 4 f SiO (4-f) / 2 [wherein each R 4 is an independently selected substituted or unsubstituted hydrocarbyl group, provided that in each molecule, at least one, or at least two, of the R 4 groups are aliphatic unsaturated groups, and f is selected such that 0 < f ≦ 3.2].

[0065] The average formula for the above organopolysiloxane can alternatively be written as (R 4 3SiO 1 / 2 ) w (R 4 2SiO 2 / 2 ) x (R 4 SiO 3 / 2 ) y (SiO 4 / 2 ) z wherein R 4and the proviso is defined above, where w, x, y, and z are independently greater than or equal to 0 and less than or equal to 1, provided that w+x+y+z=1. One of ordinary skill in the art will understand how such M, D, T, and Q units, and their mole fractions, affect the subscript f in the above average formula. The T and Q units, denoted by the subscripts y and z, are typically present in the silicone resin, while the D units, denoted by the subscript x, are typically present in the silicone polymer (and may be present in the silicone resin).

[0066] Each R 4 are independently selected as described above and may be linear, branched, cyclic, or combinations thereof. 4Suitable hydrocarbyl groups can be independently linear, branched, cyclic, or a combination thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups can be independently monocyclic or polycyclic. Linear and branched hydrocarbyl groups can independently be saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, etc., as well as derivatives, variants, and combinations thereof. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, hexadecyl, octadecyl, and branched saturated hydrocarbon groups having 6 to 18 carbon atoms. Examples of suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycloheptyl groups. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Examples of suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, hexadecenyl, octadecenyl, and cyclohexenyl groups. Examples of suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon groups or substituted halocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the above-mentioned alkyl groups in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl.Specific examples of halogenated alkyl groups include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, and derivatives thereof. Examples of halogenated aryl groups include the above-mentioned aryl groups in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl. Specific examples of halogenated aryl groups include chlorobenzyl and fluorobenzyl groups.

[0067] In certain embodiments, the organopolysiloxane is substantially linear or linear. In these embodiments, the substantially linear organopolysiloxane has the average formula: R 4 f’ SiO (4-f’) / 2 , [In the formula, each R 4 and the condition is as defined above, and f' is selected such that 1.9≦f'≦2.2.

[0068] In these embodiments, at a temperature of 25° C., the substantially linear organopolysiloxane is typically a flowable liquid or in the form of an uncured rubber. Generally, the substantially linear organopolysiloxane has a viscosity at 25° C. of 10 to 30,000,000 mPa·s, alternatively 10 to 10,000 mPa·s, alternatively 100 to 1,000,000 mPa·s, alternatively 100 to 100,000 mPa·s. As understood in the art, viscosity can be measured at 25° C. with a Brookfield LV DV-E viscometer.

[0069] In specific embodiments where the organopolysiloxane is substantially linear or linear, the organopolysiloxane has the average formula: (R 4 3SiO 1 / 2 ) m’ (R 4 2SiO 2 / 2 ) n’ (R 4 SiO 3 / 2 ) o [In the formula, each R 4 are independently selected and defined above (each molecule contains at least one R 4 is an aliphatic unsaturated group), m'≧2, n'≧0, and o≧2. In specific embodiments, m' is 2 to 10, alternatively 2 to 8, alternatively 2 to 6. In these or other embodiments, n' is 0 to 1,000, alternatively 1 to 500, alternatively 1 to 200. In these or other embodiments, o is 2 to 500, alternatively 2 to 200, alternatively 2 to 100.

[0070] The organopolysiloxane may be substantially linear, or if linear, the silicon-bonded aliphatic unsaturated group(s) may be pendant, terminal, or both pendant and terminal. Specific examples of organopolysiloxanes having pendant silicon-bonded aliphatic unsaturated groups include organopolysiloxanes having the average formula: (CH3)3SiO[(CH3)2SiO] n’ [(CH3)ViSiO] m’ Si(CH3)3 [wherein n' and m' are defined above, and Vi represents a vinyl group]. With respect to this average formula, those skilled in the art will understand that any methyl group may be replaced with a vinyl or substituted or unsubstituted hydrocarbyl group, and any vinyl group may be replaced with any ethylenically unsaturated group, as long as there are at least two aliphatic unsaturated groups in one molecule. Alternatively, as a specific example of an organopolysiloxane having terminal silicon-bonded aliphatic unsaturated groups, the organopolysiloxane may have the average formula: Vi(CH3)2SiO[(CH3)2SiO] n’ Si(CH3)2Vi where n' and Vi are defined above. Silicon-bonded vinyl-terminated dimethylpolysiloxanes can be used alone or in combination with the dimethyl, methyl-vinylpolysiloxanes disclosed above. With respect to this average formula, one skilled in the art will recognize that any methyl group may be replaced with a vinyl or substituted or unsubstituted hydrocarbyl group, and any vinyl group may be replaced with any ethylenically unsaturated group, so long as there are at least two aliphatic unsaturated groups in one molecule. Because the at least two silicon-bonded aliphatic unsaturated groups can be both pendant and terminal, the (A) organopolysiloxane can have the average formula: Vi(CH3)2SiO[(CH3)2SiO] n’ [(CH3)ViSiO] m’ SiVi(CH3)2 wherein n', m', and Vi are defined above.

[0071] The substantially linear organopolysiloxane may be a dimethylpolysiloxane terminated at both molecular chain terminals by dimethylvinylsiloxy groups, a methylphenylpolysiloxane terminated at both molecular chain terminals by dimethylvinylsiloxy groups, a methylphenylsiloxane-dimethylsiloxane copolymer terminated at both molecular chain terminals by dimethylvinylsiloxy groups, a methylvinylsiloxane-methylphenylsiloxane copolymer terminated at both molecular chain terminals by dimethylvinylsiloxy groups, or a methylvinylsiloxane-diphenylsiloxane copolymer terminated at both molecular chain terminals by dimethylvinylsiloxy groups. Examples of such polymers include methylvinylsiloxane-methylphenylsiloxane-dimethylsiloxane copolymers terminated at both molecular chain ends with dimethylvinylsiloxy groups, methylvinylsiloxane-methylphenylsiloxane copolymers terminated at both molecular chain ends with trimethylsiloxy groups, methylvinylsiloxane-diphenylsiloxane copolymers terminated at both molecular chain ends with trimethylsiloxy groups, and methylvinylsiloxane-methylphenylsiloxane-dimethylsiloxane copolymers terminated at both molecular chain ends with trimethylsiloxy groups.

[0072] In these or other embodiments, the (A) organopolysiloxane can be a resinous organopolysiloxane. In these embodiments, the resinous organopolysiloxane has the average formula: R 4 f’ SiO (4-f’’) / 2 [In the formula, each R 4 and the condition is as defined above, and f'' is selected such that 0.5≦f''≦1.7.

[0073] Resinous organopolysiloxanes have a branched or three-dimensional network molecular structure. At 25°C, the resinous organopolysiloxane may be in liquid or solid form, optionally dispersed in a carrier that can solubilize and / or disperse the resinous organopolysiloxane in the carrier.

[0074] In specific embodiments, the resinous organopolysiloxanes can be exemplified by organopolysiloxanes containing only T units, organopolysiloxanes containing T units in combination with other siloxy units (e.g., M, D, and / or Q siloxy units), or organopolysiloxanes containing Q units in combination with other siloxy units (i.e., M, D, and / or T siloxy units). Resinous organopolysiloxanes contain T and / or Q units. Specific examples of resinous polyorganosiloxanes are vinyl-functional silsesquioxanes and vinyl-functional MQ resins.

[0075] The organopolysiloxane may comprise a combination or mixture of different organopolysiloxanes, such as organopolysiloxanes of different structures.

[0076] Alternatively, the (A) unsaturated compound may be a silicone-organic hybrid. For example, the (A) unsaturated compound may comprise a hydrosilylation reaction product of an organopolysiloxane (or one or more organopolysiloxanes and one or more organic compounds), in which case the backbone of the (A) unsaturated compound may comprise an organic divalent linking group. As another example, an organohydrogensiloxane may be reacted with another organopolysiloxane or an organic compound to obtain the (A) unsaturated compound.

[0077] For example, the (A) unsaturated compound can be the reaction product of (a1) at least one Si-H compound and (b1) at least one compound having ethylenic unsaturation. In these embodiments, an excess of ethylenically unsaturated groups in the (b1) compound is utilized relative to the Si-H groups in the (a1) Si-H compound, such that the (A) unsaturated compound contains at least one, or an average of at least two, silicon-bonded aliphatic unsaturated groups.

[0078] The reaction product of the (a1) Si-H compound and the (b1) compound having ethylenic unsaturation can be called an (AB)n copolymer, and has the (a1) Si-H compound forming unit A and the (b1) compound having ethylenic unsaturation forming unit B. A combination of different (a1) Si-H compounds and a combination of different (b1) compounds having ethylenic unsaturation can be used so that the resulting (b) crosslinker contains distinct units, but cannot be an (AB)n copolymer. The distinct units can be randomized or in a blocked form.

[0079] Alternatively or additionally, (A) the unsaturated compound can include an organosilicon compound but not an organopolysiloxane, for example, (A) the unsaturated compound can include a silane, disilane, or siloxane (e.g., disiloxane) without constituting an organopolysiloxane.

[0080] An example of a suitable silane is of the formula R 5 z’’ SiR 64-z’’ wherein each R 5 are independently aliphatic unsaturated groups, and R 6 are independently substituted or unsubstituted hydrocarbyl groups, and 1≦z″≦4. An example of a siloxane is tetramethyldivinyldisiloxane. Those skilled in the art will understand how to prepare or obtain such compounds for use as (A) the unsaturated compound.

[0081] The (A) unsaturated compound can be a single unsaturated compound or a combination comprising two or more different silicon hydride compounds.

[0082] The composition and (A) unsaturated compound are subject to at least one of the following two conditions: (1) the (A) unsaturated compound also contains at least one silicon-bonded hydrogen atom per molecule, and / or (2) the composition further contains (B) a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule.

[0083] In a first embodiment, condition (1) is true, such that (A) the unsaturated compound also contains at least one silicon-bonded hydrogen atom per molecule. In a second embodiment, condition (2) is true, such that the composition further contains (B) a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule. Finally, in a third embodiment, both conditions (1) and (2) are true, such that (A) the unsaturated compound also contains at least one silicon-bonded hydrogen atom per molecule, and the composition further contains a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule.

[0084] In a first embodiment, condition (1) is true, and the (A) unsaturated compound contains at least one silicon-bonded hydrogen atom per molecule in addition to the aliphatic unsaturated group. In these embodiments, the (A) unsaturated compound can be any compound containing at least one silicon-bonded hydrogen atom and at least one aliphatic unsaturated group. In these embodiments, the (A) unsaturated compound is typically an organosilicon compound and / or an organopolysiloxane.

[0085] Those skilled in the art will readily understand how to prepare or obtain such unsaturated compounds. For example, organosilicon compounds containing both aliphatic unsaturated hydrogen and silicon-bonded hydrogen can be prepared from the unsaturated organic compounds disclosed above. By way of example only, the formula CH2=CH(CH2) b α,ω-Dienes of CH═CH₂ can be reacted with silanes of formula H₂Si(CH₃)₂ in the presence of a hydrosilylation catalyst to give silanes containing one aliphatic unsaturated group and one silicon-bonded hydrogen atom, of formula CH═CH(CH₂). b The unsaturated compound CH2CH2Si(CH3)2H can be obtained. The organosilicon compound can also be a silane, disilane, siloxane, etc. For example, the organosilicon compound can be of the formula R 5 b’ H c’ SiR 6 4-b’-c’ wherein R 5 and R 6 are independently selected and defined above, b' is 1, 2, or 3, and c' is 1, 2, or 3, provided that 2≦(b'+c')≦4.

[0086] (A) When the unsaturated compound comprises an organopolysiloxane having both aliphatic unsaturation and silicon-bonded hydrogen, the organopolysiloxane has the formula R 4 d’ H e’ SiO (4-d’-e’) / 2 wherein R 4 are independently selected and defined above (yet at least one R 4 is an aliphatic unsaturated group), and e' and f are each greater than 0 such that 0<(d'+e')≦3.2.

[0087] Alternatively, when the (A) unsaturated compound comprises an organopolysiloxane having both aliphatic unsaturation and silicon-bonded hydrogen, the silicon-bonded aliphatic unsaturated group(s) and the silicon-bonded hydrogen atom(s) may be present in any of the M, D, and / or T siloxy units present in the organopolysiloxane and may be bonded to the same silicon atom (in the case of M and / or D siloxy units). The organopolysiloxane may, for example, contain, as the M siloxy units, (R 4 3SiO 1 / 2 ), (R 4 2HSiO 1 / 2 ), (R 4 H2SiO 1 / 2 ), and / or (HSiO 1 / 2 The organopolysiloxane may contain, for example, the D siloxy unit (R 4 2SiO 2 / 2 ), (R 4 HSiO 2 / 2 ), and / or (HSiO 2 / 2 The organopolysiloxane may contain, for example, the T siloxy unit (R 4 SiO 3 / 2 ) and / or (HSiO 3 / 2 Such siloxy units may be optionally combined with Q siloxy units in any manner to form R 4 and at least one silicon-bonded hydrogen atom.

[0088] For example, the organopolysiloxane may be of the following formula: 4 2HSiO 1 / 2 ) w’ (R 4 2SiO 2 / 2 ) x’ (R 4 SiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ , (R 4 H2SiO 1 / 2 ) w’ (R 4 2SiO 2 / 2 ) x’ (R4 SiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ , (R 4 3SiO 1 / 2 ) w’ (R 4 HSiO 2 / 2 ) x’ (R 4 SiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ , (R 4 H2SiO 1 / 2 ) w’ (R 4 HSiO 2 / 2 ) x (R 4 SiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ , (R 4 3SiO 1 / 2 ) w’ (R 4 2SiO 2 / 2 ) x’ (HSiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ , (R 4 3SiO 1 / 2 ) w’ (R 4 HSiO 2 / 2 ) x’ (R 4 SiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ , and / or (R 4 H2SiO 1 / 2 ) w’ (R 4 HSiO 2 / 2 ) x’ (HSiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ and the like, wherein each R 4 are independently selected and defined above (wherein at least one R 5is an aliphatic unsaturated group), w', x', y', and z' are independently 0 to 1, provided that w'+x'+y'+z''=1.

[0089] In a second embodiment, condition (2) is true, and the composition further comprises (B) a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule. In these embodiments, the (B) silicon hydride compound can be any compound containing at least one silicon-bonded hydrogen atom. Depending on the structure of the (B) silicon hydride compound, the (B) silicon hydride compound can be a silane compound, an organosilicon compound, an organohydrogensilane, an organohydrogensiloxane, or the like.

[0090] (B) The silicon hydride compounds may have linear, branched, cyclic, resinous, or a combination of such structures. In acyclic polysilanes and polysiloxanes, the silicon-bonded hydrogen atom(s) may be located at terminal, pendant, or both terminal and pendant positions. Cyclosilanes and cyclosiloxanes typically have 3 to 12 silicon atoms, alternatively 3 to 10 silicon atoms, alternatively 3 to 4 silicon atoms.

[0091] In certain embodiments, (B) the silicon hydride compound has the formula R 7 4-s SiH s wherein R 7 is independently selected and can be any silicon-bonded group, and s is selected such that 1≦s≦4. Typically, s is 1, 2, or 3, or 1 or 2. Each R 7 are typically independently substituted or unsubstituted hydrocarbyl groups, suitable examples of which are described above. However, R may be any group as long as (B) the silicon hydride is capable of undergoing hydrosilylation through its silicon-bonded hydrogen atom. 7 can be any silicon-bonded group. For example, R 7 can be a halogen. When (B) the silicon hydride is a silane compound, (B) the silicon hydride can be a monosilane, disilane, trisilane, or polysilane.

[0092] In these or other embodiments, (B) the silicon hydride compound has the formula H g’ R 8 3-g Si-R 9 -SiR 8 2H, wherein each R 8 are independently selected substituted or unsubstituted hydrocarbyl groups, g' is 0 or 1, and R 9 is a divalent linking group. 9 is a siloxane chain (e.g., -R 8 2SiO-, -R 8 The divalent hydrocarbon group may be a siloxy group (containing -HSiO- and / or -HSiO-D siloxy units) or may be a divalent hydrocarbon group. Typically, the divalent hydrocarbon group does not contain aliphatic unsaturation. The divalent hydrocarbon group may be linear, cyclic, branched, aromatic, etc., or may have a combination of such structures.

[0093] If g' is 1, and R 9 is a divalent hydrocarbon group, specific examples of the silicon hydride compound (B) include: [ka]

[0094] In these or other embodiments, (B) the silicon hydride compound comprises an organohydrogensiloxane, which may be a disiloxane, trisiloxane, or polysiloxane. Examples of organohydrogensiloxanes suitable for use as the (B) silicon hydride compound include, but are not limited to, siloxanes having the following formula: PhSi(OSiMe2H)3, Si(OSiMe2H)4, MeSi(OSiMe2H)3, and Ph2Si(OSiMe2H)2, where Me is methyl and Ph is phenyl. Additional examples of organohydrogensiloxanes that are suitable for the purpose of (B) silicon hydride compounds include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, phenyltris(dimethylsiloxy)silane, 1,3,5-trimethylcyclotrisiloxane, trimethylsiloxy-terminated poly(methylhydrogensiloxane), trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), and dimethylhydrogensiloxy-terminated poly(methylhydrogensiloxane).

[0095] When the (B) silicon hydride compound comprises an organohydrogensiloxane, the (B) silicon hydride compound can contain any combination of M, D, T, and / or Q siloxy units, so long as the (B) silicon hydride compound contains at least one silicon-bonded hydrogen atom. These siloxy units can be combined in various ways to form cyclic, linear, branched, and / or resinous (three-dimensional network) structures. The (B) silicon hydride compound can be monomeric, polymeric, oligomeric, linear, branched, cyclic, and / or resinous, depending on the selection of M, D, T, and / or Q units.

[0096] Since the (B) silicon hydride compound contains at least one silicon-bonded hydrogen atom with respect to the siloxy unit described above, the (B) silicon hydride compound contains the following siloxy unit containing a silicon-bonded hydrogen atom: (R 8 2HSiO 1 / 2 ), (R 8 H2SiO 1 / 2 ), (HSiO 1 / 2 ), (R 8 HSiO 2 / 2), (H2SiO 2 / 2 ), and / or (HSiO 3 / 2 ), optionally in combination with siloxy units that are free of silicon-bonded hydrogen atoms, wherein R 8 are independently selected and are defined above.

[0097] In certain embodiments, for example, when the (B) silicon hydride compound is linear, the (B) silicon hydride compound has the average formula: [ka] [In the formula, each R 10 are independently hydrogen or R 8 and each R 8 are independently selected and defined above, and may have the following structure: e" > 2, f"' > 0, and g" > 2. In certain embodiments, e" is 2 to 10, alternatively, 2 to 8, alternatively, 2 to 6. In these or other embodiments, f'" is 0 to 1,000, alternatively, 1 to 500, alternatively, 1 to 200. In these or other embodiments, g" is 2 to 500, alternatively, 2 to 200, alternatively, 2 to 100.

[0098] In one embodiment, the (B) silicon hydride compound is linear and contains one or more pendant silicon-bonded hydrogen atoms. In these embodiments, the (B) silicon hydride compound may be a dimethyl, methyl hydrogen polysiloxane having the average formula: [ka] The polysiloxane may be a dimethyl, methyl-hydrogenpolysiloxane having the formula: where f''' and g'' are defined above.

[0099] In these or other embodiments, the (B) silicon hydride compound is linear and contains terminal silicon-bonded hydrogen atoms. In these embodiments, the (B) silicon hydride compound may be a SiH-terminated dimethylpolysiloxane having the average formula: [ka] where f'" is as defined above. The SiH-terminated dimethylpolysiloxane may be utilized alone or in combination with the dimethyl, methylhydrogenpolysiloxane disclosed above. Additionally, the SiH-terminated dimethylpolysiloxane may have one trimethylsiloxy terminus, such that the SiH-terminated dimethylpolysiloxane may have only one silicon-bonded hydrogen atom. Alternatively or additionally, (B) the organohydrogensiloxane may contain both pendant and terminal silicon-bonded hydrogen atoms.

[0100] In certain embodiments, the (B) silicon hydride compound may have one of the following average formulas: [ka] [In the formula, each R 11 and R 9 are independently selected and defined above, e'', f''', and g'' are defined above, h ≧ 0, and i ≧ 0. In each of the above average formulas, the subscripts sum to 1.

[0101] Some of the above average formulas for (B) silicon hydride compounds are resinous when they contain T siloxy units (denoted by the subscript h) and / or Q siloxy units (denoted by the subscript i). When the (B) silicon hydride compound is resinous, it is typically a copolymer containing T siloxy units and / or Q siloxy units in combination with M siloxy units and / or D siloxy units. For example, the organohydrogenpolysiloxane resin can be a DT resin, MT resin, MDT resin, DTQ resin, MTQ resin, MDTQ resin, DQ resin, MQ resin, DTQ resin, MTQ resin, or MDQ resin.

[0102] In various embodiments in which the (B) silicon hydride compound is resinous or comprises an organopolysiloxane resin, the (B) silicon hydride compound typically has the formula: [ka] [In the formula, each R 11 are independently H or a substituted or unsubstituted hydrocarbyl group, but at least one R 11 is H, with 0≦j′≦1, 0≦k′≦1, 0≦l′≦1, and 0≦M″≦1, where j′+k′+l′+m″=1.

[0103] In certain embodiments, the (B) silicon hydride compound generally has the formula (R 11 2SiO) r′ (R 11 HSiO) s′ [In the formula, R 11 are independently selected and defined above, r' is an integer from 0 to 7, and s' is an integer from 3 to 10. Specific examples of suitable organohydrogensiloxanes of this type include (OSiMeH), (OSiMeH), (OSiMeCH), and alkylhydrogendialkylcyclosiloxane copolymers. 13 ), (OSiMeH)2(OSiMeC6H 13 )2, and (OSiMeH)(OSiMeCH 13 )3 [wherein Me represents methyl (—CH3)].

[0104] (B) The silicon hydride compound can be a single silicon hydride compound or a combination comprising two or more different silicon hydride compounds.

[0105] Finally, in a third embodiment, both conditions (1) and (2) are true, such that (A) the unsaturated compound also contains at least one silicon-bonded hydrogen atom per molecule, and the composition further contains (B) a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule. Examples of unsaturated compounds and silicon hydride compounds suitable for this third embodiment are set forth above.

[0106] When present in the composition, (A) the unsaturated compound and (B) the silicon hydride compound may be disposed in a carrier vehicle. Examples of carrier vehicles are described below.

[0107] The present composition may contain (A) the unsaturated compound and (B) the silicon hydride compound, if present, in various amounts or ratios depending on the desired properties or end use of the composition. In various embodiments in which the present composition contains components (A) and (B), the composition contains components (A) and (B) in amounts to provide a molar ratio of silicon-bonded hydrogen atoms to aliphatic unsaturated groups of from 0.3 to 5, alternatively from 0.6 to 3.

[0108] The composition comprises (C) a catalyst and / or (C 1 (C) a redox switch catalyst system. 1 ) redox switch catalyst system, as described above, (C 1 ) may be present as a catalytic reaction product formed when converting a redox switch catalyst system to a (C) catalyst.

[0109] (C) catalyst and (C 1 The redox switch catalyst system is described above. 1 ) When a redox switch catalyst system is included, the (C) catalyst is formed in situ prior to and / or simultaneously with the formation of the composition, depending on when the reducible compound is incorporated.

[0110] (C) catalyst and / or (C 1The (C) redox switch catalyst system is present in the composition in a catalytic amount, i.e., in an amount or quantity sufficient to promote its reaction or cure under the desired conditions. 1 The catalytic amount of the (C) redox switch catalyst system can be greater than 0.01 ppm and can be greater than 1,000 ppm (e.g., up to 10,000 ppm or more). In certain embodiments, the (C) catalyst and / or (C 1 Typical catalyst amounts for the (C) redox switch catalyst system are less than 5,000 ppm, alternatively less than 2,000 ppm, alternatively less than 1,000 ppm (but in any case greater than 0 ppm). In certain embodiments, the (C) catalyst and / or (C 1 The catalytic amount of the (C) redox switch catalyst system can range from 0.01 to 1,000 ppm, alternatively from 0.01 to 100 ppm, alternatively from 0.01 to 50 ppm of metal, based on the weight of the composition. 1 ) may be related solely to the metal content within the redox switch catalyst system.

[0111] The composition may further comprise one or more optional ingredients, including adhesion promoters, carrier vehicles, dyes, pigments, antioxidants, heat stabilizers, flame retardants, flow control additives, biocides, fillers (such as extending and reinforcing fillers), surfactants, thixotropic agents, water, carrier vehicles or solvents, pH buffers, etc. The composition may be in any form, for example, incorporated into another composition as a component of the composition. For example, the composition may be in the form of an emulsion or incorporated into an emulsion. The emulsion may be an oil-in-water emulsion, a water-in-oil emulsion, a silicone-in-oil emulsion, etc. The composition itself may be the continuous or discontinuous phase of such an emulsion.

[0112] Suitable carrier vehicles are described above.

[0113] The composition comprises components (A), (B), (C), and / or (C 1) with any ingredient, in any order of addition, optionally in a masterbatch, and optionally under shear.

[0114] Also provided is a method for preparing the hydrosilylation reaction product.The hydrosilylation reaction product is formed from the present composition and can take a variety of forms depending on the section of the components in the composition.

[0115] The method comprises: 2 ) reacting an aliphatic unsaturated group and a silicon-bonded hydrogen atom in the presence of a hydrosilylation catalyst to obtain a hydrosilylation reaction product. 2 The hydrosilylation catalyst is the above-described (C) catalyst, or 1 ) redox switch catalyst system, for example, in situ. The hydrosilylation reaction product is formed by an addition reaction between a silicon-bonded hydrogen atom and an aliphatic unsaturated group. As understood in the art, hydrosilylation reactions generally occur in the case of double bonds and (C 2 In the presence of a hydrosilylation catalyst, this can be expressed as -Si-H+C=C- → -Si-CH2-CH2-. (C 2 The hydrosilylation catalysts and methods of the present invention may be utilized in any hydrosilylation reaction, for example, in place of or in addition to conventional hydrosilylation catalysts.

[0116] The aliphatic unsaturated group is present in (A) an unsaturated compound. At least one of the following two conditions applies: (1) the (A) unsaturated compound also contains at least one silicon-bonded hydrogen atom per molecule, and / or (2) the silicon-bonded hydrogen atom is present in a (B) silicon hydride compound separate from the (A) unsaturated compound. In a first embodiment, condition (1) is true, such that the (A) unsaturated compound also contains at least one silicon-bonded hydrogen atom per molecule. In a second embodiment, condition (2) is true, such that the composition further contains (B) a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule. Finally, in a third embodiment, conditions (1) and (2) are true, such that the (A) unsaturated compound also contains at least one silicon-bonded hydrogen atom per molecule, and the composition further contains (B) a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule. These embodiments are described in detail above with respect to the compositions themselves.

[0117] The hydrosilylation reaction products prepared via the present methods are not limited and are generally a function of the (A) unsaturated compound and, if utilized, the (B) silicon hydride compound. For example, the hydrosilylation reaction products can be monomeric, oligomeric, polymeric, resinous, etc. The hydrosilylation reaction products can include fluids, oils, gels, elastomers, rubbers, resins, etc. The hydrosilylation reaction products can take any form as understood in the art, based on the selection of the (A) unsaturated compound and, if utilized, the (B) silicon hydride compound.

[0118] By way of example only, the following are two reaction mechanisms that may be utilized via the method of the present invention. In these two reaction mechanisms, the method utilizes (A) 1-octene as the unsaturated compound and two different (B) silicon hydride compounds. The catalyst is the (C) catalyst described above, which may be utilized separately from the redox switch catalyst system or may be formed in situ. [ka]

[0119] In the above reaction mechanism, Ph is phenyl and Me is methyl. One skilled in the art will understand how the (A) unsaturated compound and, if utilized, (B) silicon hydride compound can be selected based on the desired target species of the hydrosilylation reaction product.

[0120] The method can be used to prepare hydrosilylated reaction products in the form of functionalized, e.g., olefin-functionalized, silanes or siloxanes, which can be utilized in other end uses, such as as separate components of other compositions, including, for example, curable compositions, personal care compositions, or cosmetic compositions.

[0121] The hydrosilylation reaction product may also include various by-products formed through the hydrosilylation reaction. For example, the hydrosilylation reaction product typically includes the target species and various by-products. The hydrosilylation reaction product may also include other components, such as a carrier or solvent, if the method and reaction are carried out therein and / or if the composition contains such components. The method may further include isolating the target species, for example, via any suitable purification method.

[0122] It is understood that the scope of the appended claims is not limited to the specific compounds, compositions, or methods described therein and may vary among specific embodiments within the scope of the appended claims. With respect to any Markush group relied upon herein to describe particular features or aspects of various embodiments, different, special, and / or unexpected results may be obtained from each member of the respective Markush group independent of all other Markush members. Each element of a Markush group may be relied upon individually and / or in combination to provide appropriate support for specific embodiments within the scope of the appended claims.

[0123] The following examples are intended to illustrate the present invention and should not be construed as limiting the scope of the invention in any way.

[0124] The various ingredients utilized in the examples are set out in Table 1 below. [Table 1-1] [Table 1-2]

[0125] The rheological measurements described below were performed on a TA Instrument DHR-3 rheometer. Each test material was placed on an Advanced Peltier plate (lower geometry) using a solvent trap. A 25 mm parallel plate was used as the upper geometry. Temperature was controlled within ±0.02°C via the Peltier system. Test parameters: strain oscillation; strain %: 1%, frequency: 1 Hz.

[0126] Preparation Example 1: Synthesis of catalyst

[0127] In a dry box, a solution of starting material (II) (1.100 g, 3.770 mmol, 4.0 equiv.) in approximately 10 mL of benzene was added dropwise to a 100 mL round-bottom flask containing a solution of starting material (I) (367 mg, 0.944 mmol, 1.0 equiv.) in approximately 15 mL of benzene to obtain a mixture. After stirring the mixture for 30 minutes, the resulting deep red-orange solution was filtered through Celite to obtain a filtrate. The volume of the filtrate was reduced in vacuo until a significant amount of precipitate appeared. The precipitate was collected by filtration as a pale pinkish-orange powder and dried in vacuo. Yield = 1.309 g, 96%. 1 H NMR(500MHz,C6D6;δ,ppm):7.77(br,8H),6.96(t,J=7.5Hz,4H),6.91(t,J=7.5Hz,8H),6.62(t,J=6.5Hz,2H),6.23(d,J=7.5Hz,2H),3.45(br,6H). 31 P{ 1H}NMR (202 MHz, C6D6; δ, ppm): 52.48 (d, JRh-P = 204.4 Hz). Single crystals suitable for X-ray crystallographic analysis were grown at room temperature from a supersaturated solution of the catalyst in THF.

[0128] Preparation Example 2: Synthesis of catalyst

[0129] In a dry box, starting material (I) (50 mg, 0.129 mmol, 1.0 equiv.) and starting material (II) (115 mg, 0.514 mmol, 4.0 equiv.) were charged into a 20 mL reaction vial. Approximately 10 mL of THF was then added. After stirring at room temperature for 1 hour, the THF was removed to give the resulting product. The resulting product was washed with diethyl ether to give a solid residue. The solid residue was redissolved in THF, and the THF was slowly evaporated to give dark maroon crystals. The crystals were filtered and dried in vacuo (yield: 72 mg, 48%). 1 H NMR (400MHz, CD2Cl2, room temperature) δ 7.59(br,2H),7.35(t,J=7.8Hz,2H),6.98(t,J=7.4Hz,4H),4.07(br,6H),2.32(br,4H),1.58-0.80(m,24H). 31 P NMR (202 MHz, CD, room temperature) δ 73.50 (d(br), J ~ 240 Hz), 60.25 (d(br), J ~ 183 Hz). Single crystals suitable for X-ray crystallographic analysis were grown at room temperature from a supersaturated solution of the catalyst in THF.

[0130] Preparation Example 3: Synthesis of redox switch catalyst

[0131] Solid initial material (I) (52 mg, 0.066 mmol, 1.0 equivalent) and initial material (II) (61 mg, 0.069 mmol, 1.05 equivalent) were charged into a 20 mL vial. Approximately 3 mL of EtO was added to the vial to obtain a yellow suspension. The yellow suspension was stirred for 1 hour to obtain the reaction product. The reaction product was orange and nearly homogeneous. The reaction product was filtered through Celite to obtain the filtrate. The filtrate was slowly evaporated to obtain orange crystals. 1H NMR(500MHz,C6D6;δ,ppm):8.44(br,8H),7.63(br,4H),7.07-6.98(m,6H),6.97-6 .90(m;8H),6.87-6.80(m,8H),6.76-6.70(m,2H),6.66-6.59(m,4H),3.63(s,6H). 13 C{ 1 H}NMR(125MHz,C6D6;δ,ppm):162.82(q,JB-C=49.5Hz),161.69(dd,J=3.3Hz),13 5.45,135.39,134.62(dd,J=4.8Hz),133.73,133.24,129.98(qm,J=31.8Hz),128 .88(dd,J=6.0Hz),126.34,125.67-124.98(m),124.49(dd,J=4.3Hz),124.17,12 2.01,119.29-118.58(m),118.15(sept,J=3.9Hz),115.88(dd,J=3.8Hz),62.34. 31 P{ 1 H}NMR (202 MHz, C6D6; δ, ppm): 37.41 (d, JRh-P = 132.5 Hz, 2P). Single crystals suitable for X-ray crystallographic analysis were grown from a supersaturated Et2O solution.

[0132] Example 1: Catalyst-Catalyzed Hydrosilylation [ka] In a drybox, a reaction vial was charged with 1,3,5-trimethoxybenzene, (A1) unsaturated compound (2.00 g, 11.47 mmol, 1 equiv.), catalyst (0.083 mg, 0.115 μmol, 0.00001 equiv., from stock solution), and (B1) silicon hydride (2.55 g, 11.47 mmol, 1 equiv.) to obtain a mixture. The mixture was removed from the drybox, connected to an argon atmosphere on a Schlenk line, and placed in a preheated oil bath (80 °C). To monitor the progress of the reaction, aliquots of the reaction mixture were taken at specific time points, as shown below, and then analyzed. 1The starting material was analyzed by H NMR spectroscopy. The conversion of the starting material was based on 1,3,5-trimethoxybenzyl. Example 1 was repeated under different curing conditions. Specifically, Example 1 was supported in C6D6 solvent (0.057 mmol for both substrates, 0.0005 equivalents of catalyst, 0.6 mL of C6D6 solvent) using neat substrate at 80 °C under an inert (nitrogen) atmosphere, neat substrate at room temperature under an inert (nitrogen) atmosphere, and at 80 °C under an inert (nitrogen) atmosphere. Tables 2-4 below show the conversion over time under various reaction conditions as indicated. In Table 2, time is measured in hours, in Table 3, time is measured in days, and in Table 4, time is measured in minutes. [Table 2] [Table 3] [Table 4] [Table 5]

[0133] Example 2: Hydrosilylation catalyzed by a redox-switch catalyst system [ka] In a dry box, (A2) unsaturated compound (17.87 mg, 159.24 μmol, 2 equivalents), redox switch catalyst (0.065 mg, 4.00 × 10 -8A J-Young NMR tube was charged with silicon hydride compound (B2) (10.85 mg, 79.62 μmol, 1 equivalent), 1,3,5-trimethoxybenzene, and 0.6 mL of deuterated benzene (CD6). After a period in a preheated water bath at 60 °C, the NMR tube was returned to the dry box, and reducing compound 1 (16 μg, 0.001 equivalent, 0.1 mol%) was added to the mixture. Upon addition of reducing compound 1, the redox-switch catalyst was observed to undergo a formal change in its oxidized state, converting in situ to a catalyst, resulting in a significant increase in conversion. The results are shown in Table 5 below, where yield is shown as a function of time. [Table 6]

[0134] Example 3: Hydrosilylation catalyzed by a redox-switch catalyst system In a dry box, (A2) unsaturated compound (17.87 mg, 159.24 μmol, 2 equivalents), redox switch catalyst (0.065 mg, 4.00 × 10 -8 A J-Young NMR tube was charged with 10.85 mg (79.62 μmol, 1 equiv.), 1,3,5-trimethoxybenzene, and 0.6 mL of deuterated benzene (CD6). After a period in a preheated water bath at 60 °C, the NMR tube was returned to the dry box, and reducing compound 2 (10 μg, 0.001 equiv.) was added to the mixture. Upon addition of reducing compound 2, the redox-switched catalyst was observed to undergo a formal change in its oxidized state, converting in situ to the catalyst, resulting in a significant increase in conversion. The results are shown in Table 6 below, where yield is shown as a function of time. [Table 7]

[0135] Example 4: Hydrosilylation catalyzed by a redox-switch catalyst system In a dry box, (A2) unsaturated compound (17.87 mg, 159.24 μmol, 2 equivalents), redox switch catalyst (0.065 mg, 4.00 × 10 -8 A J-Young NMR tube was charged with silicon hydride compound (B2) (10.85 mg, 79.62 μmol, 1 equivalent), 1,3,5-trimethoxybenzene, and 0.6 mL of deuterated benzene (CD6). After a period in a preheated water bath at 60 °C, the NMR tube was returned to the dry box, and reducing compound 3 (16 μg, 0.001 equivalent) was added to the mixture. Upon addition of reducing compound 3, the redox-switch catalyst was observed to undergo a formal change in its oxidized state, converting in situ to the catalyst, resulting in a significant increase in conversion. The results are shown in Table 7 below, where yield is shown as a function of time. [Table 8]

[0136] Example 5: Hydrosilylation of organopolysiloxanes

[0137] In a dry box, a 20 mL reaction vial was charged with (A3) unsaturated compound (1.00 g, 1 equivalent), catalyst (13 μg, 0.001 mol% to give 10 ppm mol Rh), and (B3) silicon hydride compound (2.90 g, 1 equivalent) to obtain a mixture. The mixture was removed from the dry box, connected to an argon atmosphere on a Schlenk line, and placed in a preheated oil bath (80 °C). To monitor the progress of the reaction, aliquots of the reaction mixture were taken at specific time points and analyzed. 1 The results were analyzed by H NMR spectroscopy. The conversion of the starting material was based on the consumption of unsaturation. Example 5 was repeated under different curing conditions. Specifically, Example 5 was supported at 40°C and 80°C under an inert (nitrogen) atmosphere. Table 8 below shows the conversion.

[0138] [Table 9]

[0139] Example 6: Hydrosilylation of organopolysiloxanes

[0140] In a nitrogen-filled dry box, a 20 mL reaction vial was charged with (A4) unsaturated compound (10.00 g), catalyst (0.4 mg in 40 μL of THF), and (B4) silicon hydride compound (0.96 g) to obtain a mixture. The mixture was manually stirred for approximately 200 revolutions per minute. The mixture was removed from the dry box and placed in a Dewar filled with dry ice prior to rheological measurements. In the rheometer, a portion of the sample (approximately 1 g) was transferred onto a Peltier plate under air. The experiment was initiated with a predesigned temperature switch procedure. The curing process was monitored in real time by the rheometer. The results are shown in Figure 1, which shows the storage modulus, loss modulus, and temperature as a function of time (the x-axis is time in seconds). As shown in Figure 1, increasing the temperature resulted in a significant increase in the reaction rate.

[0141] Example 7: Hydrosilylation of organopolysiloxanes

[0142] In a nitrogen-filled dry box, a 20 mL reaction vial was charged with (A4) unsaturated compound (2.5 g), catalyst (0.4 mg, 8.2 μL in THF), and (B4) silicon hydride compound (0.24 g) to obtain a mixture. The mixture was manually stirred for approximately 200 revolutions. The mixture was removed from the dry box and placed in a Dewar filled with dry ice prior to rheological measurements. In the rheometer, a portion of the sample (approximately 1 g) was transferred onto a Peltier plate under air. The curing process was monitored in real time by the rheometer. The results are shown in Figure 2, which shows the storage modulus, loss modulus, and temperature as a function of time (x-axis is time in seconds). Unlike Example 6, there was no temperature switch or ramp used in Example 7.

[0143] Comparative Example 1: Hydrosilylation of Organopolysiloxane

[0144] In a nitrogen-filled dry box, a 20 mL reaction vial was charged with (A4) unsaturated compound (5.2 g), comparative catalyst (71 μg, 7.1 μL in THF), and (B4) silicon hydride compound (0.499 g) to obtain a mixture. The mixture was manually stirred for approximately 200 revolutions. The sample was removed from the dry box and placed in a Dewar filled with dry ice prior to rheological measurements. In the rheometer, a portion of the sample (approximately 1 g) was transferred onto a Peltier plate under air. The curing process was monitored in real time by the rheometer. The results are shown in Figure 3, which shows the storage modulus, loss modulus, and temperature as a function of time (the x-axis is time in seconds). As shown in Figure 3, unlike Example 6, increasing the temperature in Comparative Example 1 did not result in a significant increase in the reaction rate.

[0145] The term "comprising" and its derivatives, such as "comprise" and "comprises," are used herein in their broadest sense to mean and encompass the notions of "including," "include," "consist(ing) essentially of," and "consist(ing) of." The use of "for example," "eg," "such as," and "including" to list examples does not limit the examples listed. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to," and encompasses other similar or equivalent examples.

[0146] Generally, as used herein, a hyphen "-" or a wavy line "~" in a range of values ​​means "to" or "through," ">" means "above" or "greater-than," "≥" means "at least" or "greater-than or equal to," "<" means "below" or "less-than," and "≤" means "at most" or "less-than or equal to." Each of the foregoing patent applications, patents, and / or patent publications is expressly incorporated herein by reference in its entirety on an individual basis in one or more non-limiting embodiments.

Claims

1. 1. A hydrosilylation catalyst, said catalyst comprising a complex having the formula: 【Chemistry 1】 wherein each R is an independently selected hydrocarbyl group, and each R １ is an independently selected aryl group and X is a halogen atom.

2. 10. A redox-switch catalyst system for preparing the catalyst of claim 1, comprising: The following formula: 【Chemistry 2】 wherein each R is an independently selected hydrocarbyl group; １ are independently selected aryl groups, each X is a halogen atom, and A is a counter anion; a reducing compound; and a redox switch catalyst system comprising:

3. 1. A method for preparing a hydrosilylation catalyst, said method comprising: reducing a redox-switch catalyst with a reducing compound to obtain said catalyst; The redox switch catalyst has the following formula: 【Transformation 3】 wherein each R is an independently selected hydrocarbyl group; １ are independently selected aryl groups, each X is a halogen atom, and A is a counter anion; The method of claim 1 , wherein the catalyst is the catalyst of claim 1 .

4. 1. A method for preparing a hydrosilylation catalyst, said method comprising: Formula [RhR ２ ２ X] ２ The starting material (I) of formula 【Chemistry 4】 to obtain the catalyst, In the formula, each R ２ are independently selected aliphatically unsaturated groups, each X is an independently selected halogen atom, R is a hydrocarbyl group, and each R １ are independently selected aryl groups; The method of claim 1 , wherein the hydrosilylation catalyst is the catalyst of claim 1 .

5. 1. A composition comprising: (A) An unsaturated compound containing at least one aliphatic unsaturated group per molecule, which satisfies the following two conditions: (1) the (A) unsaturated compound also contains at least one silicon-bonded hydrogen atom per molecule; and / or (2) the composition further comprises (B) a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule; (C) the catalyst of claim 1.

6. 1. A composition comprising: (A) An unsaturated compound containing at least one aliphatic unsaturated group per molecule, which satisfies the following two conditions: (1) the (A) unsaturated compound also contains at least one silicon-bonded hydrogen atom per molecule; and / or (2) the composition further comprises (B) a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule; (C １ 3. A composition comprising: a redox switch catalyst system according to claim 2;

7. The composition of claim 5 or 6, wherein the composition further comprises (B) a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule, and (i) the (A) unsaturated compound contains at least two unsaturated groups per molecule, (ii) the (B) silicon hydride compound contains at least two silicon-bonded hydrogen atoms per molecule, or (iii) both (i) and (ii).

8. 1. A method for preparing a hydrosilylation reaction product, the method comprising: (C ２ ) reacting an aliphatically unsaturated group and a silicon-bonded hydrogen atom in the presence of a hydrosilylation catalyst to obtain said hydrosilylation reaction product; The aliphatic unsaturated group is present in (A) an unsaturated compound and satisfies the following two conditions: (1) the (A) unsaturated compound also contains at least one silicon-bonded hydrogen atom per molecule; and / or (2) the silicon-bonded hydrogen atom is present in a silicon hydride compound (B) separate from the unsaturated compound (A); Said (C ２ 2.) The method of claim 1, wherein the hydrosilylation catalyst comprises the catalyst of claim 1.

9. 1. A method for preparing a hydrosilylation reaction product, the method comprising: (C ２ ) reacting an aliphatically unsaturated group and a silicon-bonded hydrogen atom in the presence of a hydrosilylation catalyst to obtain said hydrosilylation reaction product; The aliphatic unsaturated group is present in (A) an unsaturated compound and satisfies the following two conditions: (1) the (A) unsaturated compound also contains at least one silicon-bonded hydrogen atom per molecule; and / or (2) the silicon-bonded hydrogen atom is present in a silicon hydride compound (B) separate from the unsaturated compound (A); Said (C ２ 3.) A method wherein the hydrosilylation catalyst is formed in situ from the redox-switch catalyst system of claim 2.

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