WO2018217998A1

WO2018217998A1 - Composition and method of preparing hydrosilylation reaction product

Info

Publication number: WO2018217998A1
Application number: PCT/US2018/034353
Authority: WO
Inventors: Aswini K. Dash; Ross Fu; William A. Goddard; Robert J. NIELSEN
Original assignee: Dow Silicones Corporation; California Institute Of Technology
Priority date: 2017-05-24
Filing date: 2018-05-24
Publication date: 2018-11-29

Abstract

A composition is disclosed. The composition comprises: (A) an unsaturated compound including at least one aliphatically unsaturated group per molecule, subject to at least one of the following two provisos: (1) the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule; and/or (2) the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. The composition further comprises (C) a hydrosilylation catalyst having a specific structure. A method of preparing a hydrosilylation reaction product is also disclosed.

Description

COMPOSITION AND METHOD OF PREPARING

HYDROSILYLATION REACTION PRODUCT

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and all advantages of U.S. Patent Application No. 62/510,365 filed on 24 May 2017, the contents of which is hereby incorporated by reference.

FIELD OF THE INVENTION

[0002] The present invention generally relates to a composition and, more specifically, to a composition including a hydrosilylation catalyst and to a method of preparing a hydrosilylation-reaction product.

DESCRIPTION OF THE RELATED ART

[0003] Hydrosilylation reactions are generally known in the art and involve an addition reaction between silicon-bonded hydrogen and aliphatic unsaturation. Hydrosilylation reactions are utilized in various applications. For example, curable compositions may rely on hydrosilylation reactions for purposes of curing or crosslinking components of the curable compositions. Hydrosilylation reactions may also be utilized to prepare individual components or compounds, e.g. components for inclusion in curable compositions.

[0004] Hydrosilylation reactions are carried out in the presence of a catalyst, which is typically a platinum metal due to its excellent catalytic activity. Platinum metal is generally much more expensive than other metals with lesser catalytic activities. Generally, non- platinum catalysts suffer from instability when exposed to ambient conditions, e.g. non- platinum catalysts can be prone to undesirable side reactions with ambient oxygen and water, thereby limiting use and potential end applications thereof.

BRIEF SUMMARY OF THE INVENTION

[0005] The present invention provides a composition. The composition comprises (A) an unsaturated compound including at least one aliphatically unsaturated group per molecule, subject to at least one of the following two provisos: (1) the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule; and/or (2) the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. The composition further comprises (C) a hydrosilylation catalyst having the following structure:

wherein Z is BY2^" or PY4^"; each Y is independently F, CQF^, CQ ^, or 3,5-(CF3)2-C6H3; each E is independently CH2, NH, or O; R^ , R2 R3 and R^ are each independently selected substituted or unsubstituted hydrocarbyl groups; and [M] is M'X_nL_m, where M' is Ni,

Cu, Co, Rh, Mo, or W; X is selected from an alkyl group, a silyl group, H, an alkoxy group or a halogen atom; L is an olefin, agostic C-H, agostic Si-H, an ether, or a nitrile; n is 0 or 1; and m is 0 or 1.

[0006] A method of preparing a hydrosilylation reaction product is also provided. The method comprises reacting an aliphatically unsaturated group and a silicon-bonded hydrogen atom in the presence of (C) a hydrosilylation catalyst to give the hydrosilylation reaction product. The aliphatically unsaturated group is present in (A) an unsaturated compound; wherein at least one of the following two provisos applies: (1) the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule; and/or (2) the silicon-bonded hydrogen atom is present in (B) a silicon hydride compound separate from the (A) unsaturated compound. The (C) hydrosilylation catalyst has the following structure:

wherein Z is BY2" or PY4"; each Y is independently F, C5F5, C5H5, or 3,5-(CF3)2-CgH3; each E is independently CH2, NH, or O; R1, R2, R3 and R^ are each independently selected substituted or unsubstituted hydrocarbyl groups; and [M] is M'X_nL_m, where M' is Ni,

DETAILED DESCRIPTION OF THE INVENTION

[0007] The present invention provides a composition. The composition has excellent physical properties, including shelf life and stability. Moreover, the composition may be utilized to prepare hydrosilylation reaction products under open atmospheric conditions, as described in greater detail below. The hydrosilylation react product may be utilized in diverse end use applications.

[0008] The composition comprises (A) an unsaturated compound. The (A) unsaturated compound includes at least one aliphatically unsaturated group per molecule, which may alternatively be referred to as ethylenic unsaturation. The (A) unsaturated compound is not limited and may be any unsaturated compound having at least one aliphatically unsaturated group. In certain embodiments, the (A) unsaturated compound comprises an organic compound. In other embodiments, the (A) unsaturated compound comprises a siloxane. In yet other embodiments, the (A) unsaturated compound comprises a silicone-organic hybrid, or an organosilicon compound. Various embodiments and examples of the (A) unsaturated compound are disclosed below.

[0009] In certain embodiments, the (A) unsaturated compound includes an average of at least two aliphatically unsaturated groups per molecule. In such embodiments, the (A) unsaturated compound is capable of polymerization. The aliphatically unsaturated groups of the (A) unsaturated compound may be terminal, pendent, or in both locations in the (A) unsaturated compound.

[0010] For example, the aliphatically unsaturated group may be an alkenyl group and/or an alkynyl group. "Alkenyl group" means an acyclic, branched or unbranched, monovalent hydrocarbon group having one or more carbon-carbon double bonds. The alkenyl group may have from 2 to 30 carbon atoms, alternatively from 2 to 24 carbon atoms, alternatively from 2 to 20 carbon atoms, alternatively from 2 to 12 carbon atoms, alternatively from 2 to 10 carbon atoms, alternatively from 2 to 6 carbon atoms. Alkenyl groups are exemplified by, but not limited to, vinyl, allyl, propenyl, and hexenyl. "Alkynyl group" means an acyclic, branched or unbranched, monovalent hydrocarbon group having one or more carbon-carbon triple bonds. The alkynyl group may have from 2 to 30 carbon atoms, alternatively from 2 to 24 carbon atoms, alternatively from 2 to 20 carbon atoms, alternatively from 2 to 12 carbon atoms, alternatively from 2 to 10 carbon atoms, alternatively from 2 to 6 carbon atoms. Alkynyl is exemplified by, but not limited to, ethynyl, propynyl, and butynyl.

[0011] In specific embodiments, the (A) unsaturated compound has the formula R— Z'— R, where Z' is a divalent linking group, which may be a divalent hydrocarbon, a polyoxyalkylene, a polyalkylene, a polyisoalkylene, a hydrocarbon-silicone copolymer, a siloxane, or mixtures thereof. Z' may be linear or branched. In these specific embodiments, R is independently selected and includes aliphatic unsaturation, i.e., R is independently selected from alkenyl groups and alkynyl groups.

[0012] In these specific embodiments, the (A) unsaturated compound includes two aliphatically unsaturated groups represented by R.

[0013] In certain embodiments of the (A) unsaturated compound, Z' is a divalent hydrocarbon. The divalent hydrocarbon Z' may contain 1 to 30 carbons, either as aliphatic or aromatic structures, 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. The α,ω- unsaturated hydrocarbons may alternatively be referred to as olefins.

[0014] For example, the (A) unsaturated compound may be any diene, diyne or ene-yne compound. With reference to the formula above, in these embodiments, R may be, for example, independently selected from CH2=CH— , CH2=CHCH2— , CH2=CH(CH2)4— ,

CH2=C(CH3)CH2— or and similar substituted unsaturated groups such as H2C=C(CH3)— , and HC=C(CH3)— . In such embodiments, the (A) unsaturated compound may be referred to as an α,ω-unsaturated hydrocarbon. The α,ω-unsaturated hydrocarbon may be, for example, an α,ω-diene of the formula CH2=CH(CH2)_DCH=CH2, an α,ω-diyne of the formula

CH≡C(CH2)bC≡CH, an α,ω-ene-yne of the formula CH2=CH(CH2)bC≡CH, or mixtures thereof, where b is independently from 0 to 20.

[0015] 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-hexene-5-yne.

[0016] However, the (A) unsaturated compound may alternatively have the formula R-Z', where R and Z' are as defined above. In these specific embodiments, the (A) unsaturated compound includes one aliphatically unsaturated group represented by R.

[0017] When the (A) unsaturated compound includes only one aliphatically unsaturated group, the (A) unsaturated compound may be referred to as an unsaturated hydrocarbon, and may be any -eye 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 include aryl groups so long as the (A) unsaturated compound also includes the at least one aliphatically unsaturated group independent from any aryl groups.

[0018] In another embodiment, the (A) unsaturated compound comprises, alternatively is, a polyether. In these embodiments, the (A) unsaturated compound comprises a polyoxyalkylene group having the formula (C_aH2_aO), wherein subscript a is from 2 to 4. With reference to the general formula above, Z' is the polyoxyalkylene group. In these embodiments, the (A) unsaturated compound may be referred to as the polyoxyalkylene.

[0019] The polyoxyalkylene may comprise 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.

[0020] For example, the (A) unsaturated compound as the polyoxyalkylene may have the following general formula:

RO-[(C₂H40)_c(C3H₆0)_d(C₄H₈0)e]-R

wherein each R is independently selected and defined above, c is from 0 to 200, d is from 0 to 200, and e is from 0 to 200, with the proviso that c, d and e are not simultaneously 0. In specific embodiments, c is from 0 to 50, alternatively from 0 to 10, alternatively from 0 to 2. In these or other embodiments, d is from 0 to 100, alternatively 1 to 100, alternatively 5 to 50. In these or other embodiments, e is from 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 greater than 0.8, or alternatively greater than 0.95.

[0021] This polyoxyalkylene is terminated at each molecular chain end (i.e. alpha and omega positions) with R, which is independently selected and described above. Additional examples of R include H₂C=C(CH₃)CH₂— H₂C=CHCH₂CH₂— , H₂C=CHCH₂CH₂CH₂— , and H₂C=CHCH₂CH₂CH₂CH₂— , HC≡C— , HC≡CCH₂— , HC≡CCH(CH3)— , HC≡CC(CH3)₂— , HC≡CC(CH3)₂CH₂— . However, the polyoxyalkylene set forth above is merely one exemplary example of a suitable polyoxyalkylene.

[0022] In specific embodiments, the polyoxyalkylene group comprises only oxypropylene units (0₃ΗβΟ). Representative, non-limiting examples of polyoxypropylene-containing polyoxyalkylenes include: H₂C=CHCH₂[C₃H60]_dCH₂CH=CH₂,

H₂C=CH[C₃H₆0]_dCH=CH_2> H₂C=C(CH3)CH₂[C₃H₆0]_dCH₂C(CH₃)=CH₂,

HC≡CCH₂[C₃H₆0]_dCH₂C=CH, and HC≡CC(CH₃)₂[C₃H₆0]_dC(CH₃)₂C≡CH, where d is as defined above.

[0023] Representative, non-limiting examples of polyoxybutylene or poly(oxytetramethylene) containing polyoxyalkylenes include: H₂C=CHCH₂[C4H80]_eCH₂CH=CH₂,

H₂C=CH[C₄H80]_eCH=CH₂, H₂C=C(CH₃)CH₂[C₄H80]_eCH₂C(CH₃)=CH₂,

HC≡CCH₂[C₄H₈0]eCH2C≡CH, and HC≡CC(CH₃)₂[C₄H₈0]_eC(CH₃)₂C≡CH, where e is as defined above.

[0024] The examples of polyoxyalkylenes suitable for the (A) unsaturated compound include two aliphatically unsaturated groups. However, the polyoxyalkylene suitable for the (A) unsaturated compound may include only one aliphatically unsaturated group. For example, the polyoxyalkylene suitable for the (A) unsaturated compound may alternatively have the following general formula:

RO-[(C₂H₄0)_c(C₃H₆0)_d(C₄H₈0)_e]- R'

where R, c, d, and e are as defined above, and R' is H or an alkyl group, such as CH₃. Any description or examples above also apply to this embodiment as well. One of skill in the art readily understands how the examples of polyoxyalkylenes above with two aliphatically unsaturated groups may alternatively include but one aliphatically unsaturated group.

[0025] The polyoxyalkylene may be prepared by, for example, the polymerization of ethylene oxide, propylene oxide, butylene oxide, 1 ,2-epoxyhexane, 1 ,2-epoxyoctance, and/or cyclic epoxides, such as cyclohexene oxide or exo-2,3-epoxynorborane. The polyoxyalkylene moiety of the polyoxyalkylene may comprise oxyethylene units (C₂H₄0), oxypropylene units (ΟβΗβΟ), oxybutylene units (C4H80), or mixtures thereof. Typically, the polyoxyalkylene group comprises a majority of oxypropylene or oxybutylene units, as defined on a molar basis and indicated in the above formula by the c, d, and e subscripts.

[0026] In another embodiment, Z' of the general formula R— Z'— R or of the formula R-Z' of the (A) unsaturated compound comprises a polyalkylene group. The polyalkylene group may comprise from C2 to CQ alkylene units or their isomers. One specific example is polyisobutylene group, which is a polymer including isobutylene units. For example, the (A) unsaturated compound may be a di-allyl terminated polyisobutylene or an allyl-terminated polyisobutylene. The molecular weight of the polyisobutylene group may vary, but typically ranges from 100 to 10,000 g/mole.

[0027] In certain embodiments, the (A) unsaturated compound comprises an organopolysiloxane. The organopolysiloxane is not limited and may be any organopolysiloxane including at least one silicon-bonded aliphatically unsaturated group per molecule. For example, the organopolysiloxane may be linear, branched, partly branched, cyclic, resinous (i.e., have a three-dimensional network), or may comprise a combination of different structures. When the (A) unsaturated compound comprises the organopolysiloxane, the aliphatically unsaturated group is silicon-bonded (e.g. as silicon-bonded alkenyl and/or silicon-bonded alkynyl).

[0028] In certain embodiments when the (A) unsaturated compound comprises an organopolysiloxane, the organopolysiloxane has the following average formula:

R⁵fSiO(4-f)/2

wherein each R^ is an independently selected substituted or unsubstituted hydrocarbyl group with the proviso that in each molecule, at least one, alternatively at least two, R5 groups is an aliphatically unsaturated group, and wherein f is selected such that 0 < f≤ 3.2.

[0029] The average formula above for the organopolysiloxane may be alternatively written as (R¾SiOi/2)w(R¾Si02/2)x(R¾03/2)y(Si04/2)_z, where R^ and its proviso is defined above, and w, x, y, and z are independently from≥0 to≤1, with the proviso that w+x+y+z=1. One of skill in the art understands how such M, D, T, and Q units and their molar fractions influence subscript f in the average formula above. T and Q units, indicated by subscripts y and z, are typically present in silicone resins, whereas D units, indicated by subscript x, are typically present in silicone polymers (and may also be present in silicone resins).

[0030] Each R^ is independently selected, as introduced above, and may be linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups encompass aryl groups as well as saturated or non-conjugated cyclic groups. Aryl groups may be monocyclic or polycyclic. Linear and branched hydrocarbyl groups may independently be saturated or unsaturated. One example of a combination of a linear and cyclic hydrocarbyl group is an aralkyl group.

[0031] Substituted hydrocarbyl groups are hydrocarbyl groups having one or more atoms (e.g. C and/or H) replaced (i.e., substituted) with another atom or substituent (i.e., group), for example, a halogen atom such as chlorine, fluorine, bromine or iodine, an oxygen atom, an oxygen atom containing group such as an acrylic, methacrylic, alkoxy, or carboxyl group, a nitrogen atom, a nitrogen atom containing group such as an amino, amido, or cyano group, a sulphur atom, or a sulphur atom containing group such as a mercapto group. Examples of substituted hydrocarbyl groups include propyl groups substituted with chlorine or fluorine, such as 3,3,3-trifluoropropyl groups, chloro- and alkoxy-phenyl groups, beta- (perfluorobutyl)ethyl groups, chlorocyclohexyl groups, and heteroaryls such as pyridinyl groups.

[0032] Hydrocarbyl groups may be exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, or similar alkyl groups; vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, cyclohexenyl, or similar alkenyl groups; phenyl, tolyl, xylyl, naphthyl, or similar aryl groups; benzyl, phenethyl, or similar aralkyl groups; and 3-chloropropyl, 2-bromoethyl, 3,3,3- trifluoropropyl, or similarly substituted (e.g. halogenated) alkyl groups.

[0033] Examples of the aliphatically unsaturated group(s) represented by R are introduced above.

[0034] In certain embodiments, the organopolysiloxane is substantially linear, alternatively is linear. In these embodiments, the substantially linear organopolysiloxane may have the average formula:

R⁵fSiO(4__f)/2

wherein each R^ and its proviso are as defined above, and wherein f is selected such that 1.9≤f≤2.2.

[0035] In these embodiments, at a temperature of 25 °C, the substantially linear organopolysiloxane is typically a flowable liquid or is in the form of an uncured rubber. Generally, the substantially linear organopolysiloxane has a viscosity of from 10 to 30,000,000 mPa-s, alternatively from 10 to 10,000 mPa-s, alternatively from 100 to 1,000,000 mPa-s, alternatively from 100 to 100,000 mPa-s, at 25 °C. Viscosity may be measured at 25 °C via a Brookfield LV DV-E viscometer, as understood in the art.

[0036] In specific embodiments in which the organopolysiloxane is substantially linear or linear, the organopolysiloxane may have the average formula:

(R53Si0₁/2)_m-(R⁵2Si0₂/2)n^,(R⁵Si03/2)o, wherein each is independently selected and defined above (including the proviso that in each molecule, at least one is an aliphatically unsaturated group), and m'≥2, n'≥0, and o≥2. In specific embodiments, m' is from 2 to 10, alternatively from 2 to 8, alternatively from 2 to 6. In these or other embodiments, n' is from 0 to 1,000, alternatively from 1 to 500, alternatively from 1 to 200. In these or other embodiments, o is from 2 to 500, alternatively from 2 to 200, alternatively from 2 to 100.

[0037] When the organopolysiloxane is substantially linear, alternatively is linear, the silicon- bonded aliphatically unsaturated group(s) may be pendent, terminal or in both pendent and terminal locations. As a specific example of the organopolysiloxane having pendant silicon- bonded aliphatically unsaturated groups, the organopolysiloxane may have the average formula:

(CH₃)3SiO[(CH3)2SiO]_n. [(CH3)ViSiO]_m.Si(CH₃)3 where n' and m' are as defined above, and Vi indicates a vinyl group. With regard to this average formula, one of skill in the art knows that any methyl group may be replaced with a vinyl or a substituted or unsubstituted hydrocarbyl group, and any vinyl group may be replaced with any ethylenically unsaturated group, so long as at least two aliphatically unsaturated groups are present per molecule. Alternatively, as a specific example of the organopolysiloxane having terminal silicon-bonded aliphatically unsaturated groups, the organopolysiloxane may have the average formula:

Vi(CH₃)2SiO[(CH3)₂SiO]_n-Si(CH3)2Vi

where n' and Vi are as defined above. The dimethyl polysiloxane terminated with silicon- bonded vinyl groups may be utilized alone or in combination with the dimethyl, methyl-vinyl polysiloxane disclosed immediately above. With regard to this average formula, one of skill in the art knows that any methyl group may be replaced with a vinyl or a substituted or unsubstituted hydrocarbyl group, and any vinyl group may be replaced with any ethylenically unsaturated group, so long as at least two aliphatically unsaturated groups are present per molecule. Because the at least two silicon-bonded aliphatically unsaturated groups may be both pendent and terminal, the (A) organopolysiloxane may have the average formula:

Vi(CH₃)2SiO[(CH3)2SiO]_n.[(CH3)ViSiO]_m.SiVi(CH₃)2 where n', m' and Vi are as defined above.

[0038] The substantially linear organopolysiloxane can be exemplified by a dimethylpolysiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a methylphenylpolysiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylphenylsiloxane and dimethylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane and a methylphenylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane and diphenylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane, methylphenylsiloxane, and dimethylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane and a methylphenylsiloxane capped at both molecular terminals with trimethylsiloxy groups, a copolymer of a methylvinylsiloxane and diphenylsiloxane capped at both molecular terminals with trimethylsiloxy groups, and a copolymer of a methylvinylsiloxane, methylphenylsiloxane, and a dimethylsiloxane capped at both molecular terminals with trimethylsiloxy groups.

[0039] In these or other embodiments, the (A) organopolysiloxane may be a resinous organopolysiloxane. In these embodiments, the resinous organopolysiloxane may have the average formula:

R⁵f^»SiO(4_f)/2

wherein each and its provisos are as defined above, and wherein f ' is selected such that 0.5≤f'≤ 1.7.

[0040] The resinous organopolysiloxane has a branched or a three dimensional network molecular structure. At 25 °C, the resinous organopolysiloxane may be in a liquid or in a solid form, optionally dispersed in a carrier, which may solubilize and/or disperse the resinous organopolysiloxane therein.

[0041] In specific embodiments, the resinous organopolysiloxane may be exemplified by an organopolysiloxane that comprises only T units, an organopolysiloxane that comprises T units in combination with other siloxy units (e.g. M, D, and/or Q siloxy units), or an organopolysiloxane comprising Q units in combination with other siloxy units (i.e., M, D, and/or T siloxy units). Typically, the resinous organopolysiloxane comprises T and/or Q units. A specific example of the resinous organopolysiloxane is a vinyl-terminated silsesquioxane.

[0042] The organopolysiloxane may comprise a combination or mixture of different organopolysiloxanes, including those of different structures.

[0043] Alternatively, the (A) unsaturated compound may be a silicone-organic hybrid. For example, the (A) unsaturated compound may comprise the hydrosilylation reaction product of organopolysiloxanes (or of one or more organopolysiloxanes with one or more organic compounds), in which case the backbone of the (A) unsaturated compound may include organic divalent linking groups. As another example, organohydrogensiloxanes may be reacted with other organopolysiloxanes, or with organic compounds, to give the (A) unsaturated compound. [0044] For example, the (A) unsaturated compound may be the reaction product of (a1) at least one Si-H compound and (b1) at least one compound having ethylenic unsaturation. In these embodiments, a molar excess of ethylenic unsaturated groups of the (b1 ) compound are utilized as compared to Si-H groups of the (a1) Si-H compound such that the (A) unsaturated compound includes at least one, alternatively an average of at least two, silicon- bonded aliphatically unsaturated groups.

[0045] The reaction product of the (a1) Si-H compound and the (b1) compound having ethylenic unsaturation may be referred to as an (AB)n type copolymer, with the (a1 ) Si-H compound forming units A and the (b1) compound having ethylenic unsaturation forming units B. Combinations of different (a1) Si-H compounds may be utilized, and combinations of different (b1) compounds having ethylenic unsaturation may be utilized, such that the resulting (b) crosslinking agent comprises distinct units but may not be an (AB)n type copolymer. The distinct units may be randomized or in block form.

[0046] Alternatively still, the (A) unsaturated compound may comprise an organosilicon- compound, but not an organopolysiloxane. For example, the (A) unsaturated compound may comprise a silane, a disilane, or a siloxane (for example a disiloxane), while not constituting an organopolysiloxane.

[0047] One example of a suitable silane is that of formula R^_Z"S^'\R^^._Z", where each R6 independently is an aliphatically unsaturated group, R⁷ is independently a substituted or unsubstituted hydrocarbyl group, and 1 ≤ z" ≤ 4. One example of a siloxane is tetramethyldivinyldisiloxane. One of skill in the art understands how to prepare or obtain such compounds for use as the (A) unsaturated compound.

[0048] The (A) unsaturated compound can be a single unsaturated compound or a combination comprising two or more different silicon hydride compounds.

[0049] The composition and (A) unsaturated compound are subject to at least one of the following two provisos: (1) the (A) unsaturated compound also includes at least one silicon- bonded hydrogen atom per molecule; and/or (2) the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.

[0050] In a first general embodiment, the proviso (1) is true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule. In a second general embodiment, the proviso (2) is true such that the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. Finally, in a third general embodiment, both proviso (1 ) and proviso (2) are true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule, and that the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.

[0051] In the first general embodiment, the proviso (1) is true and the (A) unsaturated compound includes at least one silicon-bonded hydrogen atom per molecule in addition to the aliphatically unsaturated group. In these embodiments, the (A) unsaturated compound may be any compound including at least one silicon-bonded hydrogen atom and at least one aliphatically unsaturated group. In these embodiments, the (A) unsaturated compound is typically an organosilicon compound and/or an organopolysiloxane.

[0052] One of skill in the art readily understands how to prepare or obtain such unsaturated compounds. For example, organosilicon compounds including both aliphatic unsaturated and silicon-bonded hydrogen may be prepared from the unsaturated organic compounds disclosed above. As but one example, an α,ω-diene of the formula CH2=CH(CH2) CH=CH2 may be reacted with a silane of formula H2Si(CH3)2 in the presence of a hydrosilylation catalyst to give an unsaturated compound of formula CH2=CH(CH2) CH2CH2Si(CH3)2H, which includes one aliphatically unsaturated group and one silicon-bonded hydrogen atom. The organosilicon compound may also be a silane, disilane, siloxane, etc. For example, the organosilicon compound may be of formula R^b'^c'SiR^-b'-c'- ^wnere R6 and R7 are independently selected and defined above, b' is 1 , 2, or 3, c' is 1 , 2, or 3, with the proviso that 2≤ (b'+c')≤4.

[0053] When the (A) unsaturated compound comprises the organopolysiloxane having both aliphatic unsaturation and silicon-bonded hydrogen, the organopolysiloxane may have the formula R^d'He'S'O^-d'-e')^- where R^ is independently selected and defined above (still subject to the proviso that at least one R⁵ is the aliphatically unsaturated group), and e' and f are each greater than 0 such that 0 < (d'+e¹)≤ 3.2.

[0054] Alternatively, when the (A) unsaturated compound comprises the organopolysiloxane having both aliphatic unsaturation and silicon-bonded hydrogen, the silicon-bonded aliphatically unsaturated group(s) and the silicon-bonded hydrogen atom(s) may be present in any M, D, and/or T siloxy unit 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 comprise, for example, as M siloxy units: (R¾SiOi/2), (R¾HSiO-|/2), (R^H2SiO-|/2), and/or

(H3SiO<|/2). The organopolysiloxane may comprise, for example, as D siloxy units:

(R52S1O2/2). (R^HSi02/2). and/or (F^SiC^^)- The organopolysiloxane may comprise, for example, as T siloxy units: (R^Si03/2) and/or (HS1O3/2). Such siloxy units may be combined in any manner, optionally along with Q siloxy units, to give an organopolysiloxane having at least one silicon-bonded aliphatically unsaturated group designated by R⁵ and at least one silicon-bonded hydrogen atom.

[0055] For example, the organopolysiloxane may have any one of the following formulas:

(R52HSi0₁/2)w^l(R⁵2Si02/2)x^l(R⁵Si03/2)y-(Si0₄/2)_z-,

(R5H2Si0₁/2)w^l(R⁵2Si02/2)x^l(R⁵Si03/2)y-(Si0₄/2)_z-,

(R53Si0₁/2)w^l(R⁵HSi02/2)x^l(R⁵Si03/2)y-(Si0₄/2)_z-,

(R5H2Si0₁/2)w^l(R⁵HSi02/2)x^l(R⁵Si03/2)y-(Si0₄/2)_z-,

(R53Si0₁/2)_w-(R⁵2Si02/2)x^l(HSi03/2)y-(Si0₄/2)_z-,

(R53Si0₁/2)_w-(R⁵HSi02/2)x^l(R⁵Si0₃/2)y-(Si04/2)_z-, and/or

(R⁵H2SiOi/2)_w'(R⁵HSi02/2)x^,(HSi03/2)y'(Si04/2)_z ⁱ, etc., where each R⁵ is independently selected and defined above (with at least one R⁵ being an aliphatically unsaturated group), and w', x', y', and z' are independently from≥0 to≤1 , with the proviso that w'+x'+y'+z' -l .

[0056] In the second general embodiment, the proviso (2) is true and the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. In these embodiments, the (B) silicon hydride compound may be any compound including at least one silicon-bonded hydrogen atom. Depending on a structure of the (B) silicon hydride compound, the (B) silicon hydride compound may be a silane compound, an organosilicon compound, an organohydrogensilane, an organohydrogensiloxane, etc.

[0057] The (B) silicon hydride compound can be linear, branched, cyclic, resinous, or have a combination of such structures. In acyclic polysilanes and polysiloxanes, the silicon-bonded hydrogen atom(s) can be located at terminal, pendant, or at both terminal and pendant positions. Cyclosilanes and cyclosiloxanes typically have from 3 to 12 silicon atoms, alternatively from 3 to 10 silicon atoms, alternatively from 3 to 4 silicon atoms.

[0058] In certain embodiments, the (B) silicon hydride compound is of formula R^.gSiHs, where R8 is independently selected and may be any silicon-bonded group, and s is selected such that 1 ≤ s≤ 4. Typically, s is 1, 2, or 3, alternatively 1 or 2. Each R** is typically independently a substituted or unsubstituted hydrocarbyl group. However, R^ can be any silicon-bonded group so long as the (B) silicon hydride is still capable of undergoing hydrosilylation via its silicon-bonded hydrogen atom. For example, R** can be a halogen. When the (B) silicon hydride is a silane compound, the (B) silicon hydride can be a monosilane, disilane, trisilane, or polysilane. [0059] In these or other embodiments, the (B) silicon hydride compound may be an organosilicon compound of formula:

wherein each R9 IS an independently selected substituted or unsubstituted hydrocarbyl group, g' is 0 or 1, and R10 is a divalent linking group. R^O may be a siloxane chain (including, for example, -R^SiO-, -

R^HSiO-, and/or -h^SiO- D siloxy units) or may be a divalent hydrocarbon group. Typically, the divalent hydrocarbon group is free of aliphatic unsaturation. The divalent hydrocarbon group may be linear, cyclic, branched, aromatic, etc., or may have combinations of such structures.

[0060] When g' is 1, and when R10 is a divalent hydrocarbon group, specific examples of the B) silicon hydride compound include:

[0061] In these or other embodiments, the (B) silicon hydride compound comprises an organohydrogensiloxane, which can 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 formulae: PhSi(OSiMe2H)3,

Si(OSiMe2H)4, MeSi(OSiMe2H)3, and Ph2Si(OSiMe2H)2, wherein Me is methyl, and Ph is phenyl. Additional examples of organohydrogensiloxanes that are suitable for purposes of the (B) silicon hydride compound include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3- tetraphenyldisiloxane, phenyltris(dimethylsiloxy)silane, 1,3,5-trimethylcyclotrisiloxane, a trimethylsiloxy-terminated poly(methylhydrogensiloxane), a trimethylsiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane), and a dimethylhydrogensiloxy-terminated poly(methylhydrogensiloxane).

[0062] When the (B) silicon hydride compound comprises an organohydrogensiloxane, the (B) silicon hydride compound may comprise any combination of M, D, T and/or Q siloxy units, so long as the (B) silicon hydride compound includes at least one silicon-bonded hydrogen atom. These siloxy units can be combined in various manners to form cyclic, linear, branched and/or resinous (three-dimensional networked) structures. The (B) silicon hydride compound may be monomeric, polymeric, oligomeric, linear, branched, cyclic, and/or resinous depending on the selection of M, D, T, and/or Q units.

[0063] Because the (B) silicon hydride compound includes at least one silicon-bonded hydrogen atom, with reference to the siloxy units set forth above, the (B) silicon hydride compound may comprise any of the following siloxy units including silicon-bonded hydrogen atoms, optionally in combination with siloxy units which do not include any silicon-bonded hydrogen atoms: (R⁹2HSiO^<|/2), (R⁹H2SiO^<|/2), (H3S1O1/2), (R⁹HSiC>2/2). (H2S1O2/2), and/or (HS1O3/2), where R⁹ is independently selected and defined above.

[0064] In specific embodiments, for example when the (B) silicon hydride compound is linear, the (B) silicon hydride compound may have the average formula:

(Rl l3Si0₁/2)e"(R⁹2Si02/2)f"(R⁹HSi0₂/2)g", wherein each R11 is independently hydrogen or R⁹ each R⁹ is independently selected and defined above, and e"≥2, f"≥0, and g"≥2. In specific embodiments, e" is from 2 to 10, alternatively from 2 to 8, alternatively from 2 to 6. In these or other embodiments, f " is from 0 to 1 ,000, alternatively from 1 to 500, alternatively from 1 to 200. In these or other embodiments, g" is from 2 to 500, alternatively from 2 to 200, alternatively from 2 to 100.

[0065] In certain embodiments, the (B) silicon hydride compound is linear and includes one or more pendent silicon-bonded hydrogen atoms. In these embodiments, the (B) silicon hydride compound may be a dimethyl, methyl-hydrogen polysiloxane having the average formula;

(CH3)₃SiO[(CH3)2SiO]f^»[(CH3)HSiO]g^»Si(CH3)3 where f " and g" are as defined above.

[0066] In these or other embodiments, the (B) silicon hydride compound is linear and includes terminal silicon-bonded hydrogen atoms. In these embodiments, the (B) silicon hydride compound may be an SiH terminal dimethyl polysiloxane having the average formula:

H(CH3)2SiO[(CH3)₂SiO]f^»Si(CH3)2H

where f " is as defined above. The SiH terminal dimethyl polysiloxane may be utilized alone or in combination with the dimethyl, methyl-hydrogen polysiloxane disclosed immediately above. Further, the SiH terminal dimethyl polysiloxane may have one trimethylsiloxy terminal such that the SiH terminal dimethyl polysiloxane may have only one silicon-bonded hydrogen atom. Alternatively still, the (B) organohydrogensiloxane may include both pendent and terminal silicon-bonded hydrogen atoms.

[0067] In certain embodiments, the (B) silicon hydride compound may have one of the following average formulas:

(Rl l3Si0₁/2)e"(R⁹2Si02/2)f"(R⁹HSi02/2)g"(R⁹Si0₃/2)h.

(Rl l3Si0₁/2)e"(R⁹2Si02/2)f"(R⁹HSi02/2)g(Si0₄/2)i,

(Rl l3Si0₁/2)e"(R⁹2Si02/2)f"(R⁹HSi02/2)g"(R⁹Si03/2)h(Si0₄/2)i, wherein each and R⁹ is independently selected and defined above, e", f ", and g" are as defined above, and h≥0, and i is≥0. In each of the average formulas above, the sum of the subscripts is 1.

[0068] Some of the average formulas above for the (B) silicon hydride compound are resinous when the (B) silicon hydride compound includes T siloxy units (indicated by subscript h) and/or Q siloxy units (indicated by subscript i). When the (B) silicon hydride compound is resinous, the (B) silicon hydride compound is typically a copolymer including 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, an MT resin, an MDT resin, a DTQ resin, an MTQ resin, an MDTQ resin, a DQ resin, an MQ resin, a DTQ resin, an MTQ resin, or an MDQ resin.

[0069] 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:

(Rl23Si0₁/2)j-(R¹²2Si02/2)k^,(R¹²Si03/2)r(Si0₄/2)_m" (IV) wherein each R12 independently is H or a substituted or unsubstituted hydrocarbyl group, with the proviso that in one molecule, at least one R^ js H; and wherein 0≤j'≤1; 0≤k'≤1;0≤l'≤1;and 0≤m"≤1; with the proviso that j'+k'+l'+m'^l

[0070] In certain embodiments, the (B) silicon hydride compound may comprise an alkylhydrogen cyclosiloxane or an alkylhydrogen dialkyl cyclosiloxane copolymer, represented in general by the formula (R^SiOJr-iR^HSiOJs', where R12 js independently selected and defined above, and where r' is an integer from 0-7 and s' is an integer from 3- 10. Specific examples of suitable organohydrogensiloxanes of this type include (OSiMeH)4,

(OSiMeH)₃(OSiMeC₆H ₃), (OSiMeH)₂(OSiMeC₆H ₃)2, and (OSiMeH)(OSiMeC₆H ₃)₃, where Me represents methyl (— CH3). [0071] The (B) silicon hydride compound can be a single silicon hydride compound or a combination comprising two or more different silicon hydride compounds.

[0072] Finally, in a third general embodiment, both proviso (1 ) and proviso (2) are true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule, and the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. Examples of suitable unsaturated compounds and silicon hydride compounds for this third general embodiment are set forth above.

[0073] The (A) unsaturated compound, as well as the (B) silicon hydride compound, if present in the composition, may be disposed in a carrier vehicle. Examples thereof are described below in connection with optional components for the composition itself.

[0074] The composition may comprise the (A) unsaturated compound and the (B) silicon hydride compound, when present, in varying amounts or ratios contingent on desired properties or end use application of the composition. In various embodiments when the composition comprises components (A) and (B), the composition comprises components (A) and (B) in an amount to provide a mole ratio of silicon-bonded hydrogen atoms to aliphatically unsaturated groups of from 0.3 to 5, alternatively from 0.6 to 3.

[0075] The composition further comprises (C) a hydrosilylation catalyst. The (C) hydrosilylation catalyst has the following structure:

wherein Z is BY2^" or PY4^"; each Y is independently F, CQF^, CQH$, or 3,5-(CF3)2-C6H3; each E is independently CH2, NH, or O; R1 , R2, R3 and R^ are each independently selected substituted or unsubstituted hydrocarbyl groups; and [M] is M'X_nL_m, where M' is Ni,

Cu, Co, Rh, Mo, or W; X is selected from an alkyl group, a silyl group, H, an alkoxy group or a halogen atom; L is an olefin, agostic C-H, agostic Si-H, an ether, or a nitrile; n is 0 or 1 ; and m is 0 or 1.

[0076] As introduced above, Z is BY2^" or PY4^", and each Y is independently F, CQF$, C5H5, or 3,5-(CF3)2-CgH3. In certain embodiments, Y is independently F, C5F5, or 3,5-

(CF3)2-CgH3. Accordingly, in some embodiments, Z is BY2^". In these embodiments, Z may be BF₂ ^". B(C₆F₅)₂-, B(3,5-(CF₃)2-C₆H₃)2-, BF(C₆F₅)-, BF(3,5-(CF₃)2-C₆H₃)- B(C₆F₅)(3,5-(CF3)2-C₆H₃)-, B(C₆H₅)₂-, BF(C₆H₅)-, B(C₆H₅)(3,5-(CF3)2-C₆H₃)-

In other embodiments, Z is PY4^", where each Y is independently selected and defined above. In certain embodiments, Z is PF4^".

[0077] Each E is independently CH2, NH, or O. Accordingly, depending on a selection of each E, the (C) hydrosilylation catalyst may have any one of the following general structures:

wherein Z, R^-R^, and [M] are as defined above.

[0078] Each of R^, R^, R3 and R^ is independently selected, as introduced above, and may be linear, branched, cyclic, or combinations thereof. Suitable examples of substituted and unsubstituted hydrocarbyl groups are as defined above.

[0079] In certain embodiments, each of R^, R^, R3 and R4 is independently selected based on a factor such as steric hindrance, electronics (e.g. electron donative, inductive, or withdrawing effects), and the like, or combinations thereof. In particular embodiments, one or more of R1, R2, R3 and R^ is selected to impart chirality on the (C) hydrosilylation catalyst.

In other embodiments, each of R^, R2 R3 and R4 is independently selected to impart symmetry on the (C) hydrosilylation catalyst. In these or other embodiments, each of R1, R2,

R3 and R4 may be independently selected to enforce reactive regioselectivity, such as anti- Markovnikov selectivity.

[0080] In some embodiments, each of R^, R2 R3 and R^ is independently selected from t- butyl and phenyl groups. In these embodiments, the (C) hydrosilylation catalyst may be further defined as having one of the following structures:

wherein Z, E, and [M] are as defined above.

[0081] As introduced above, [M] of the (C) hydrosilylation catalyst has formula M'X_nL_m, where M' is a metal selected from Ni, Cu, Co, Rh, Mo, and W; X is an alkyl group, a silyl group, H, an alkoxy group, or a halogen atom; L is an olefin, agostic C-H, agostic Si-H, an ether, or a nitrile; n is 0 or 1 ; and m is 0 or 1.

[0082] In certain embodiments, n and m are both 1 such that the (C) hydrosilylation catalyst has the following structure:

wherein Z, E, R1-R4, IVl', X, and L are as defined above. In these or other embodiments, X and L may bond together to form various moieties associated with M'XL. For example, in certain embodiments the (C) hydrosilylation catalyst may have the following structure:

wherein R13 and R14 are each independently selected substituted or unsubstituted hydrocarbyl, silyl, or siloxane groups.

[0083] In certain embodiments, n is 1 and m is 0, such that the (C) hydrosilylation catalyst has the following structure:

wherein Z, E, R^ -R^, M', and X are as defined above. In these embodiments, X may be a halogen atom such as fluorine (F), chlorine (CI), bromine (Br), or iodine (I); an alkyl group such as any of the alkyl and alkyl-containing hydrocarbyl groups described herein; a silyl group such as a mono-, di-, or trialkylsilyl group; or an alkoxy group. When X is an alkoxy group, the (C) hydrosilylation catalyst has the following structure:

wherein R15 js an alkyl group, such as any of the alkyl and alkyl-containing hydrocarbyl groups described herein.

[0084] In particular embodiments, R15 js a t-butyl group. In other embodiments, X is a trimethylsilyl (TMS) group. In further embodiments, X is H. In particular embodiments, X is a silyl group formed from the (A) unsaturated compound or the (B) silicon hydride compound, as described in greater detail below in connection with the method of the present invention.

[0085] In certain embodiments, n is 0 and m is 1 such that the (C) hydrosilylation catalyst may be further defined as having the followin structure:

wherein Z, E, R^-R^, M', and L are as defined above. As introduced above, L is an olefin, agostic C-H, agostic Si-H, an ether, or a nitrile. In specific embodiments, L is an olefin of the (A) unsaturated compound, as described in greater detail below in connection with the method of the present invention.

[0086] The (C) hydrosilylation-reaction catalyst may be in or on a solid carrier. Examples of carriers include activated carbons, silicas, silica aluminas, aluminas, zeolites and other inorganic powders/particles (e.g. sodium sulphate), and the like. The (C) hydrosilylation- reaction catalyst may also be disposed in a vehicle, e.g. a solvent which solubilizes the (C) hydrosilylation-reaction catalyst, alternatively a vehicle which merely carries or disperses, but does not solubilize, the (C) hydrosilylation-reaction catalyst. Such vehicles are known in the art.

[0087] A combination of different hydrosilylation-reaction catalysts may be utilized. For example, the composition may further comprise one or more supplemental catalysts in combination with the (C) hydrosilylation-reaction catalyst.

[0088] If utilized, the supplemental catalyst typically comprises a Group 8 to Group 11 transition metal. Group 8 to Group 11 transition metals refer to the modern lUPAC nomenclature. Group 8 transition metals are iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs); Group 9 transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir); Group 10 transition metals are nickel (Ni), palladium (Pd), and platinum (Pt); and Group 11 transition metals are copper (Cu), silver (Ag), and gold (Au). Combinations thereof, complexes thereof (e.g. organometallic complexes), and other forms of such metals may be utilized as the supplemental catalyst.

[0089] Additional examples of catalysts suitable for the supplemental catalyst include rhenium (Re), molybdenum (Mo), Group 4 transition metals (i.e., titanium (Ti), zirconium (Zr), and/or hafnium (Hf)), lanthanides, actinides, and Group 1 and 2 metal complexes (e.g. those comprising calcium (Ca), potassium (K), strontium (Sr), etc.). Combinations thereof, complexes thereof (e.g. organometallic complexes), and other forms of such metals may be utilized as the supplemental catalyst.

[0090] The supplemental catalyst may be in any suitable form. For example, the supplemental catalyst may be a solid, examples of which include platinum-based catalysts, palladium-based catalysts, and similar noble metal-based catalysts, and also nickel-based catalysts. Specific examples thereof include nickel, palladium, platinum, rhodium, cobalt, and similar elements, and also platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, nickel-molybdenum, and similar catalysts comprising combinations of a plurality of metals. Additional examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu- Fe-AI, Cu-Zn-Ti, and similar copper-containing catalysts, and the like.

[0091] In specific embodiments, the supplemental catalyst comprises platinum. In these embodiments, the supplemental catalyst is exemplified by, for example, platinum black, compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, a reaction product of chloroplatinic acid and a monohydric alcohol, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum chloride, and complexes of such compounds with olefins or organopolysiloxanes, as well as platinum compounds microencapsulated in a matrix or core- shell type compounds. Microencapsulated hydrosilylation catalysts and methods of their preparation are also known in the art, as exemplified in U.S. Patent Nos. 4,766,176 and 5,017,654, which are incorporated by reference herein in their entireties.

[0092] Complexes of platinum with organopolysiloxanes suitable for use as the supplemental catalyst include 1,3-diethenyl-1,1 ,3,3-tetramethyldisiloxane complexes with platinum. These complexes may be microencapsulated in a resin matrix. Alternatively, the supplemental catalyst may comprise 1 ,3-diethenyl-1 ,1 ,3,3-tetramethyldisiloxane complex with platinum. The supplemental catalyst may be prepared by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound such as divinyltetramethyldisiloxane, or alkene-platinum-silyl complexes. Alkene-platinum-silyl complexes may be prepared, for example by mixing 0.015 mole (COD)PtCl2with 0.045 mole COD and 0.0612 moles HMeSiC^.

[0093] The supplemental catalyst may also, or alternatively, be a photoactivatable hydrosilylation catalyst, which may initiate curing via irradiation and/or heat. The photoactivatable hydrosilylation catalyst can be any hydrosilylation catalyst capable of catalyzing the hydrosilylation reaction, particularly upon exposure to radiation having a wavelength of from 150 to 800 nanometers (nm).

[0094] Typically, however, the composition includes the (C) hydrosilylation-reaction catalyst, but not the supplemental catalyst.

[0095] The (C) hydrosilylation-reaction catalyst is present in the composition in a catalytic amount, i.e., an amount or quantity sufficient to promote a reaction or curing thereof at desired conditions. The catalytic amount of the (C) hydrosilylation-reaction catalyst may be greater than 0.01 ppm, and may be greater than 1,000 ppm (e.g., up to 10,000 ppm or more). In certain embodiments, the typical catalytic amount of (C) hydrosilylation-reaction catalyst is 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 specific embodiments, the catalytic amount of the (C) hydrosilylation-reaction catalyst may range from 0.01 to 1,000 ppm, alternatively 0.01 to 100 ppm, and alternatively 0.01 to 50 ppm of metal based on the weight of the composition.

[0096] The composition may further comprise one or more optional components, including adhesion promoters, carrier vehicles, dyes, pigments, anti-oxidants, heat stabilizers, flame retardants, flow control additives, biocides, fillers (including extending and reinforcing fillers), surfactants, thixotroping agents, water, carrier vehicles or solvents, pH buffers, etc. The composition may be in any form and may be incorporated into further compositions, e.g. as a component of a composition. For example, the composition may be in the form of, or incorporated into, an emulsion. The emulsion may be an oil-in-water emulsion, water-in-oil emulsion, silicone-in-oil emulsion, etc. The composition itself may be a continuous or discontinuous phase of such an emulsion.

[0097] Suitable carrier vehicles include silicones, both linear and cyclic, organic oils, organic solvents and mixtures of these. Specific examples of solvents may be found in U.S. Pat. No. 6,200,581, which is hereby incorporated by reference for this purpose.

[0098] Typically, the carrier vehicle, if present, is an organic liquid. Organic liquids includes those considered oils or solvents. The organic liquids are exemplified by, but not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols having more than 3 carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides and aromatic halides. Hydrocarbons include, isododecane, isohexadecane, Isopar L (C11-C13), Isopar H (C11-C12), hydrogenated polydecene. Ethers and esters include isodecyl neopentanoate, neopentylglycol heptanoate, glycol distearate, dicapr lyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3 ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methylether acetate (PGMEA), propylene glycol methylether (PGME), octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate/dicaprate, octyl ether, and octyl palmitate. Additional organic carrier fluids suitable as a stand-alone compound or as an ingredient to the carrier fluid include fats, oils, fatty acids, and fatty alcohols.

[0099] The carrier vehicle may also be a low viscosity organopolysiloxane or a volatile methyl siloxane or a volatile ethyl siloxane or a volatile methyl ethyl siloxane having a viscosity at 25° C in the range of 1 to 1 ,000 mm^/sec, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, ecamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, exadeamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3, bis{(trimethylsilyl)oxy}trisiloxane pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane as well as polydimethylsiloxanes, polyethylsiloxanes, polymethylethylsiloxanes, polymethylphenylsiloxanes, polydiphenylsiloxanes, caprylyl methicone, and any mixtures thereof.

[00100] The composition may be prepared by combining components (A)-(C), along with any optional components, in any order of addition, optionally with a master batch, and optionally under shear.

[00101] A method of preparing a hydrosilylation reaction product is also provided. The hydrosilylation reaction product is formed from the composition and may take a variety of forms depending on a section of the components in the composition.

[00102] The method comprises reacting an aliphatically unsaturated group and a silicon- bonded hydrogen atom in the presence of the (C) hydrosilylation catalyst to give the hydrosilylation reaction product.

[00103] The aliphatically unsaturated group is present in the (A) unsaturated compound. At least one of the following two provisos applies: (1) the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule; and/or (2) the silicon- bonded hydrogen atom is present in the (B) silicon hydride compound separate from the (A) unsaturated compound. In a first general embodiment, the proviso (1) is true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule. In a second general embodiment, the proviso (2) is true such that the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. Finally, in a third general embodiment, both proviso (1) and proviso (2) are true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule, and that the composition further comprises the (B) silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. These embodiments are described in detail above with respect to the composition itself.

[00104] The aliphatically unsaturated group and the silicon-bonded hydrogen atom react in the presence of the (C) hydrosilylation reaction catalyst. In embodiments of the (C) hydrosilylation catalyst where n and m are both 0, the (C) hydrosilylation catalyst typically comprises a free coordination site. In such embodiments, the (A) unsaturated compound and/or the (B) silicon hydride compound may interact with the (C) hydrosilylation catalyst, and thus become X or L as defined above. Likewise, the (A) unsaturated compound and/or the (B) silicon hydride compound may interact with the (C) hydrosilylation catalyst by displacing X or L, and thus become X or L as defined above via substitution. Moreover, if the (A) unsaturated compound and/or the (B) silicon hydride compound interact with and become X and/or L of the (C) hydrosilylation catalyst, the components of the composition may begin to react along a catalytic pathway.

[00105] In particular, without being bound to any particular theory, it is believed that the aliphatically unsaturated group and the silicon-bonded hydrogen atom react in the presence of the (C) hydrosilylation catalyst via mechanisms that do not involve formal changes in oxidation state. In other words, the (C) hydrosilylation catalyst remains in one formal oxidation state while enabling two independent bond rearrangements. In particular embodiments, an initial (C) hydrosilylation catalyst contains a metal-carbon bond (e.g. X is an alkyl) and undergoes a metathesis reaction with the silicon-bonded hydrogen atom to form the hydrosilylation reaction product and generate another of (or regenerate) the (C) hydrosilylation catalyst. The particular (C) hydrosilylation catalyst generated depends on the catalytic pathway followed.

[00106] In the (C) hydrosilylation catalyst generated, X is either a silyl group (i.e., a metal - silane intermediate) formed via oxidative hydride migration or X is H (i.e., a metal-hydride intermediate) formed via silyl group migration.

[00107] More specifically, when X is a silyl group, the metal-silane intermediate reacts with another of the aliphatically unsaturated group (e.g. via olefin insertion). During this olefin insertion, the covalent metal-silane bond is replaced by a metal-carbon bond and a carbon- silane bond. Thereafter, another of the (B) silicon hydride compound interacts with the (C) hydrosilylation catalyst (e.g. via coordination and/or oxidative addition), the hydrosilylation reaction product is formed via reductive elimination, and another of the (C) hydrosilylation catalyst is thereby formed.

[00108] When X is H, the metal-hydrogen intermediate reacts with another of the aliphatically unsaturated group (i.e., olefin insertion). During this olefin insertion, the covalent metal-hydrogen bond is replaced by a metal-carbon bond and a carbon-hydrogen bond. Thereafter, another of the (B) silicon hydride compound interacts with the (C) hydrosilylation catalyst (e.g. via coordination and/or oxidative addition), the hydrosilylation reaction product is formed via reductive elimination, and another of the (C) hydrosilylation catalyst is thereby formed.

[00109] These alternative mechanisms are generally shown below for illustrative purposes only when the (A) unsaturated compound has formula R-Z' or R-Z'-R:

Oxidative Silyl group

hydride migration migration

(a) (b)

where M' is defined above; Z" is 71 or Z'-R, where 71 and R are as defined above; and L' is of the formula (R¹)(R²)PEZEP(R³)(R⁴), where R¹-R⁴, E, and Z are as defined above.

[00110] Not only does the (C) hydrosilylation catalyst not change oxidation states while catalyzing the hydrosilylation reaction, but the (C) hydrosilylation catalyst is generally stable it atmospheric conditions, e.g. conditions in which ambient oxygen and water are present. As such, in certain embodiments, the method is carried out in an open air atmosphere. When the method is carried out in a reactor, e.g. a closed reactor, inert gases are not required. Moreover, the method may be carried out at any temperature. In particular embodiments, the method is carried out at room temperature and/or an elevated temperature. In some embodiments, the reaction is carried out at a temperature in the range of from 20 to 150 °C, such as from 20 to 145, 20 to 140, 20 to 135, 20 to 130, 25 to 130, 25 to 125, 30 to 125, 35 to 120, 40 to 115, 45 to 110, or 50 to 100, °C. In certain embodiments, the method is carried out at multiple different temperatures, such as a combination of any two or more temperatures within any of the ranges of temperatures listed above.

[00111] The hydrosilylation-reaction product prepared via the method is not limited and is generally a function of the (A) unsaturated compound and, if utilized, the (B) silicon hydride compound. For example, the hydrosilylation-reaction product may be monomeric, oligomeric, polymeric, resinous, etc. The hydrosilylation-reaction product may comprise a fluid, an oil, a gel, an elastomer, a rubber, a resin, etc. The hydrosilylation-reaction product may take any form.

[00112] The method may be utilized to prepare hydrosilylation-reaction products in the form of functionalized, e.g. olefin functionalization, silanes or siloxanes. Such functionalized silanes or siloxanes may be utilized in other end use applications, e.g. as a discrete component in another composition, including a curable composition, a personal care or cosmetic composition, etc.

[00113] The hydrosilylation-reaction product may also include various byproducts formed via the hydrosilylation reaction. For example, the hydrosilylation-reaction product typically includes a target species and various byproducts. The hydrosilylation-reaction product may also include other components, e.g. a carrier or solvent, if the method and reaction is carried out therein and/or if the composition includes such components. The method may further comprise isolating the target species from the various byproducts, e.g. via any suitable purification method.

[00114] The (C) hydrosilylation catalyst and inventive method can be utilized in any hydrosilylation reaction, e.g. in lieu of or in addition to conventional hydrosilylation catalysts. The (C) hydrosilylation catalyst is generally less expensive than conventional hydrosilylation catalysts based on platinum, while still having excellent catalytic activity.

[00115] It is to be understood that the appended claims are not limited to express and particular compounds, compositions, or methods described in the detailed description, which may vary between particular embodiments which fall within the scope of the appended claims. With respect to any Markush groups relied upon herein for describing 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 from all other Markush members. Each member of a Markush group may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims. [00116] Further, any ranges and subranges relied upon in describing various embodiments of the present invention independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein. One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on. As just one example, a range "of from 0.1 to 0.9" may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims. In addition, with respect to the language which defines or modifies a range, such as "at least," "greater than," "less than," "no more than," and the like, it is to be understood that such language includes subranges and/or an upper or lower limit. As another example, a range of "at least 10" inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims. Finally, an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims. For example, a range "of from 1 to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

[00117] The following examples are intended to illustrate the invention and are not to be viewed in any way as limiting to the scope of the invention.

EXAMPLES

Prophetic Hydrosilylation Reaction 1 :

[00118] A reaction vessel equipped for stirring is charged with an (A) unsaturated compound including at least one aliphatically unsaturated group and at least one silicon- bonded hydrogen atom per molecule ((CH2CHSi(CH3)OCH3); 1eq.). A solution of the (C) hydrosilylation catalyst ([F2B(OP^tBu2)2.Ni-C2H3Si(CH3)20CH3; 0.05 eq.) in toluene is added to the reaction vessel to form a mixture, and the mixture is stirred for 24 hr to give a hydrosilylation reaction product having the formula

CH2CHSi(CH3)(OCH3)[CH2CH2Si(CH3)(OCH3)]_n»CH2CH₂Si(CH3)(OCH3)H. Prophetic Hvdrosilylation Reaction 2:

[00119] A reaction vessel is charged with an (A) unsaturated compound including at least one aliphatically unsaturated group per molecule (dimethylvinylmethoxysilane; 1eq) and a (B) silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule (trimethylsilane; 1eq). A solution of the (C) hydrosilylation catalyst

(Ρ4Ρ(ΟΡΡ^Βυ)2]Οο-θ2Η38ί(ΟΗ3)2θΟΗ3; 0.05 eq.) in toluene is added to the reaction vessel to form a mixture, and the mixture is stirred for 24 hr to give a hydrosilylation reaction product having the formula (CH3)3SiCH2CH2Si(CH3)20CH3.

[00120] The invention has been described in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. Obviously, many modifications and variations of the present invention are possible in light of the above teachings. The invention may be practiced otherwise than as specifically described.

Claims

CLAIMS What is claimed is:

1. A composition, comprising:

(A) an unsaturated compound including at least one aliphatically unsaturated group per molecule, subject to at least one of the following two provisos:

(1) the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule; and/or

(2) the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule; and

(C) a hydrosilylation catalyst having the following structure:

wherein Z is BY2^" or PY4^"; each Y is independently F, C5F5, C5H5, or 3,5-(CF3)2-

C6H3; each E is independently CH2, NH, or O; R^, R2 R3 and R^ are each independently selected substituted or unsubstituted hydrocarbyl groups; and [M] is M'X_nL_m, where M' is Ni,

2. The composition of claim 1 , wherein proviso (2) is true such that composition further comprises (B) the silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.

3. The composition of claim 2, wherein: (i) the (A) unsaturated compound includes at least two unsaturated groups per molecule; (ii) the (B) silicon hydride compound includes at least two silicon-bonded hydrogen atoms per molecule; or (iii) both (i) and (ii).

4. A method of preparing a hydrosilylation reaction product, comprising:

reacting an aliphatically unsaturated group and a silicon-bonded hydrogen atom in the presence of (C) a hydrosilylation catalyst to give the hydrosilylation reaction product; wherein the aliphatically unsaturated group is present in (A) an unsaturated compound; wherein at least one of the following two provisos applies:

(1) the (A) unsaturated compound also includes at least one silicon- bonded hydrogen atom per molecule; and/or

(2) the silicon-bonded hydrogen atom is present in (B) a silicon hydride compound separate from the (A) unsaturated compound; and wherein the (C) hydrosilylation catalyst has the following structure:

wherein Z is BY2^" or PY4^"; each Y is independently F, CQF^, CQH$, or 3,5-(CF3)2- C5H3; each E is independently CH2, NH, or O; R1 , R2, R3 and R^ are each independently selected substituted or unsubstituted hydrocarbyl groups; and [M] is M'X_nL_m, where M' is Ni,

5. The method of claim 4, wherein: (i) the (C) hydrosilylation catalyst does not exhibit a change in oxidation state; (ii) the method is carried out in ambient atmospheric conditions; or (iii) both (i) and (ii).

6. The method of claim 4 or 5, wherein n is 1 and m is 1.

7. The method of any one of claims 4 to 6, wherein the (C) hydrosilylation catalyst forms a metal-carbon bond, and wherein the method further comprises:

forming a metal-silane intermediate via oxidative hydride migration; and

forming the hydrosilylation-reaction product with the metal-silane intermediate, thereby regenerating a metal-carbon bond.

8. The method of any one of claims 4 to 6, wherein the (C) hydrosilylation catalyst forms a metal-carbon bond, and wherein the method further comprises:

forming a metal-hydride intermediate via silyl group migration; and

forming the hydrosilylation-reaction product with the metal- hydride intermediate, thereby regenerating a metal-carbon bond.

9. The method of any one of claims 4 to 8, wherein proviso (2) is true such that the silicon-bonded hydrogen atom is present in (B) the silicon hydride compound different from the (A) unsaturated compound.

10. The method of claim 9, wherein: (i) the (A) unsaturated compound includes at least two unsaturated groups per molecule; (ii) the (B) silicon hydride compound includes at least two silicon-bonded hydrogen atoms per molecule; or (iii) both (i) and (ii).

11. The hydrosilylation-reaction product formed in accordance with the method of any one of claims 4 to 10.