WO2013043785A2 - Nickel containing hydrosilylation catalysts and compositions containing the catalysts - Google Patents

Nickel containing hydrosilylation catalysts and compositions containing the catalysts Download PDF

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Publication number
WO2013043785A2
WO2013043785A2 PCT/US2012/056202 US2012056202W WO2013043785A2 WO 2013043785 A2 WO2013043785 A2 WO 2013043785A2 US 2012056202 W US2012056202 W US 2012056202W WO 2013043785 A2 WO2013043785 A2 WO 2013043785A2
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Prior art keywords
ring structure
general formula
group
ligand
hydrogen
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PCT/US2012/056202
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French (fr)
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WO2013043785A3 (en
Inventor
Kurt Brandstadt
Simon Cook
Binh Thanh Nguyen
Avril Surgenor
Richard Taylor
Ming-Shin Tzou
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Dow Corning Corporation
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Application filed by Dow Corning Corporation filed Critical Dow Corning Corporation
Priority to JP2014530966A priority Critical patent/JP6101695B2/en
Priority to US14/232,965 priority patent/US9545624B2/en
Priority to CN201280045402.2A priority patent/CN103814040B/en
Priority to EP12775358.0A priority patent/EP2758416B8/en
Priority to PCT/US2012/056202 priority patent/WO2013043785A2/en
Publication of WO2013043785A2 publication Critical patent/WO2013043785A2/en
Publication of WO2013043785A3 publication Critical patent/WO2013043785A3/en

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    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
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Definitions

  • hydrosilylation catalysts for catalyzing hydrosilylation reaction are known in the art and are commercially available.
  • Such conventional hydrosilylation catalysts can be a metal selected from platinum, rhodium, ruthenium, palladium, osmium, and iridium.
  • the hydrosilylation catalyst may be a compound of such a metal, for example, chloroplatinic acid, chloroplatinic acid hexahydrate, platinum dichloride, and complexes of said compounds with low molecular weight organopolysiloxanes or platinum compounds microencapsulated in a matrix or core/shell type structure.
  • Complexes of platinum with low molecular weight organopolysiloxanes include 1 ,3-diethenyl-1 ,1 ,3,3 -tetramethyldisiloxane complexes with platinum. These complexes may be microencapsulated in a resin matrix.
  • Exemplary hydrosilylation catalysts are described in U.S. Patents 3,159,601 ; 3,220,972; 3,296,291 ; 3,419,593; 3,516,946; 3,814,730; 3,989,668; 4,784,879; 5,036,1 17; and 5,175,325 and EP 0 347 895 B.
  • Microencapsulated hydrosilylation catalysts and methods of preparing them are known in the art, as exemplified in U.S. Patents 4,766,176 and 5,017,654.
  • hydrosilylation catalysts suffer from the drawback of being extremely costly. Some of the metals in these hydrosilylation catalysts may also be difficult to obtain, and some of these hydrosilylation catalysts may be difficult to prepare. There is a need in industry to replace the conventional hydrosilylation catalysts described above with a less expensive and/or more readily available alternative.
  • a reaction product of ingredients comprising a Nickel precursor (Ni precursor) and a ligand, and methods for preparation of the reaction product are disclosed.
  • composition which is capable of forming a reaction product via hydrosilylation reaction, comprises the reaction product and an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction.
  • the aliphatically unsaturated compound lacks a silicon bonded hydrogen atom
  • the composition further comprises an SiH functional compound having an average, per molecule, of one or more silicon bonded hydrogen atoms.
  • disclosure of a range of, for example, 2.0 to 4.0 includes the subsets of, for example, 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7, and 3.8 to 4.0, as well as any other subset subsumed in the range.
  • disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein.
  • disclosure of the Markush group a hydrogen atom , an alkyi group, an aryl group, or an aralkyl group includes the member alkyi individually; the subgroup alkyi and aryl; and any other individual member and subgroup subsumed therein.
  • Alkyi means an acyclic, branched or unbranched, saturated monovalent hydrocarbon group. Alkyi is exemplified by, but not limited to, methyl, ethyl, propyl (e.g., iso-propyl and/or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and/or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and/or tert-pentyl), hexyl, heptyl, octyl, nonyl, and decyl, as well as branched saturated monovalent hydrocarbon groups of 6 or more carbon atoms.
  • propyl e.g., iso-propyl and/or n-propyl
  • butyl e.g., isobutyl, n-butyl, tert-
  • Aryl means a cyclic, fully unsaturated, hydrocarbon group.
  • Aryl is exemplified by, but not limited to, cyclopentadienyl, phenyl, anthracenyl, and naphthyl.
  • Monocyclic aryl groups may have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms.
  • Polycyclic aryl groups may have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, and alternatively 12 to 14 carbon atoms.
  • Aralkyl means an alkyi group having a pendant and/or terminal aryl group or an aryl group having a pendant alkyi group.
  • exemplary aralkyl groups include tolyl, xylyl, benzyl, phenylethyl, phenyl propyl, and phenyl butyl.
  • Carbocycle and “carbocyclic” each mean a hydrocarbon ring.
  • Carbocycles may be monocyclic or alternatively may be fused, bridged, or spiro polycyclic rings.
  • Monocyclic carbocycles may have 3 to 9 carbon atoms, alternatively 4 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms.
  • Polycyclic carbocycles may have 7 to 1 7 carbon atoms, alternatively 7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms.
  • Carbocycles may be saturated or partially unsaturated.
  • Cycloalkyl means saturated carbocycle.
  • Monocyclic cycloalkyl groups are exemplified by cyclobutyl, cyclopentyl, and cyclohexyl.
  • Halogenated hydrocarbon means a hydrocarbon where one or more hydrogen atoms bonded to a carbon atom have been formally replaced with a halogen atom.
  • Halogenated hydrocarbon groups include haloalkyl groups, halogenated carbocyclic groups, and haloalkenyl groups.
  • Haloalkyl groups include fluorinated alkyi groups such as trifluoromethyl (CF3), fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4- trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3- nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl; and chlorinated alkyl groups such as chloromethyl and 3-chloropropyl.
  • fluorinated alkyi groups such as trifluoromethyl (CF3), fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3,3,3-triflu
  • Halogenated carbocyclic groups include fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4- difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl; and chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl.
  • Haloalkenyl groups include allyl chloride.
  • Heteroatom means any of the Group 13-17 elements of the lUPAC Periodic Table of the Elements at
  • Heteroatom include, for example, N, O, P, S, Br, CI, F, and I.
  • Heteroatom containing group means an organic group comprised of a carbon atom and that also includes at least one heteroatom.
  • Heteroatom containing groups may include, for example, one or more of acyl, amide, amine, carboxyl, cyano, epoxy, hydrocarbonoxy, imino, ketone, ketoxime, mercapto, oxime, and/or thiol.
  • the heteroatom containing group may be a halogenated hydrocarbon group as defined above.
  • the heteroatom when the heteroatom is oxygen, then the heteroatom containing group may be a hydrocarbonoxy group such as an alkoxy group or an alkylalkoxy group.
  • Inorganic heteroatom containing group means group comprised of at least 1 heteroatom and at least 1 of hydrogen or a different heteroatoms.
  • Heteroatom containing groups may include, for example, one or more of amine, hydroxyl, imino, nitro, oxo, sulfonyl, and/or thiol.
  • Heteroalkyl means an acyclic, branched or unbranched, saturated monovalent hydrocarbon group that also includes at least one heteroatom.
  • Heteroalkyl includes haloalkyl groups and alkyl groups in which at least one carbon atom has been replaced with a heteroatom such as N, O, P, or S, e.g., when the heteroatom is O, the heteroalkyl group may be an alkoxy group.
  • Heterocycle and “heterocyclic” each mean a ring group comprised of carbon atoms and one or more heteroatoms in the ring.
  • the heteroatom in the heterocycle may be N, O, P, S, or a combination thereof.
  • Heterocycles may be monocyclic or alternatively may be fused, bridged, or spiro polycyclic rings.
  • Monocyclic heterocycles may have 3 to 9 member atoms in the ring, alternatively 4 to 7 member atoms, and alternatively 5 to 6 member atoms.
  • Polycyclic heterocycles may have 7 to 17 member atoms, alternatively 7 to 14 member atoms, and alternatively 9 to 10 member atoms.
  • Heterocycles may be saturated or partially unsaturated.
  • Heteroaromatic means a fully unsaturated ring containing group comprised of carbon atoms and one or more heteroatoms in the ring.
  • Monocyclic heteroaromatic groups may have 5 to 9 member atoms, alternatively 6 to 7 member atoms, and alternatively 5 to 6 member atoms.
  • Polycyclic heteroaromatic groups may have 10 to 17 member atoms, alternatively 10 to 14 member atoms, and alternatively 12 to 14 member atoms.
  • Heteroaromatic includes heteroaryl groups such as pyridyl.
  • Heteroaromatic includes heteroaralkyl, i.e., an alkyl group having a pendant and/or terminal heteroaryl group or a heteroaryl group having a pendant alkyl group.
  • Exemplary heteroaralkyl groups include methylpyridyl and dimethylpyridyl.
  • FTIR means Fourier transform infrared spectroscopy.
  • GC gas chromatography.
  • GPC gel permeation chromatography.
  • Mn means number average molecular weight. Mn may be measured using GPC.
  • Mw means weight average molecular weight.
  • NMR nuclear magnetic resonance.
  • Pa s means Pascal seconds, and "ppm” means parts per million.
  • COD means cyclooctadienyl.
  • Et means ethyl.
  • Me means methyl.
  • Ph means phenyl.
  • Pr means propyl and includes various structures such as iPr and nPr.
  • iPr means isopropyl.
  • nPr means normal propyl.
  • Bu means butyl and includes various structures including nBu, sec-butyl, tBu, and iBu.
  • iBu means isobutyl.
  • nBu means normal butyl.
  • tBu means tert-butyl.
  • AcAc means acetyl acetonate.
  • 2- EHA means 2-ethylhexanoate.
  • OAc means acetate.
  • Hex means hexenyl.
  • THF means tetrahydrofuran.
  • Vi means vinyl.
  • M-unit means a siloxane unit having formula R3S1O-1 /2, where each R independently represents a monovalent atom or organic group.
  • D-unit means a siloxane unit having formula R2Si02/2 > where each R independently represents a monovalent atom or group.
  • T-unit means a siloxane unit having formula RS1O3/2, where each R independently represents a monovalent atom or group.
  • Q-unit means a siloxane unit having formula S1O4/2.
  • Non-functional means that the ingredient does not have either an aliphatically unsaturated substituent or a silicon bonded hydrogen atom that participates in a hydrosilylation reaction.
  • the composition described herein may be free of platinum catalysts.
  • “Free of platinum catalysts” means that the composition contains a non-detectable amount of a platinum catalyst capable of catalyzing a hydrosilylation reaction with the unsaturated groups on other ingredients in the composition, or the composition contains an amount of a platinum catalyst insufficient to change the GC measurement measured as described in the Examples section, as compared to the same composition with the platinum catalyst omitted.
  • the composition may be free of conventional metal catalysts.
  • Free of conventional metal catalysts means that the composition contains a non-detectable amount of a the metal selected from Pt, Rh, Ru, Pd, Os, and Ir, or the compound of such a metal capable of catalyzing a hydrosilylation reaction with the unsaturated groups on other ingredients in the composition, or the composition contains an amount of the conventional metal catalyst insufficient to change the GC measurement measured as described in the Examples section, as compared to the same composition with the conventional metal catalyst omitted.
  • composition described herein may be free of hydrosilylation reaction catalysts (i.e., free of any ingredient capable of catalyzing a hydrosilylation reaction of the aliphatically unsaturated groups on ingredient (B), described below, other than ingredient (A) described herein).
  • composition which has at least one ingredient capable of reacting by hydrosilylation reaction (composition), comprises:
  • the Nicontaining hydrosilylation reaction catalyst is characterizable as being effective for catalyzing the hydrosilylation reaction of the composition.
  • the hydrosilylation reaction of the composition prepares a reaction product.
  • the reaction product may have a form selected from the group consisting of a silane, a gum, a gel, a rubber, and a resin.
  • the composition further comprises ingredient (C), an SiH functional compound having an average, per molecule, of one or more silicon bonded hydrogen atoms, which is distinct from ingredients (A) and (B).
  • the composition may optionally further comprise one or more additional ingredients, which are distinct from ingredient (A), ingredient (B), and ingredient (C) described above.
  • additional ingredients are exemplified by (D) a spacer; (E) an extender, a plasticizer, or a combination thereof; (F) a filler; (G) a filler treating agent; (H) a biocide; (I) a stabilizer, (J) a flame retardant; (K) a surface modifier; (L) a chain lengthener; (M) an endblocker; (N) a flux agent; (O) an anti-aging additive; (P) a pigment; (Q) an acid acceptor (R) a rheological additive; (S) a vehicle; (T) a surfactant; (U) a corrosion inhibitor; and a combination thereof.
  • Ingredient (A) is a Ni containing hydrosilylation reaction catalyst.
  • the Ni containing hydrosilylation reaction catalyst comprises, or is prepared with, the reaction product of the Ni precursor and the ligand. Without wishing to be bound by theory, it is thought that this reaction product comprises a Ni-ligand complex.
  • the Ni precursor is distinct from the Ni-ligand complex.
  • the Ni precursor is distinct from the reaction product of the Ni precursor and the ligand.
  • the Ni precursor may be a metal compound having general formula (i): N1-A2, where each A is independently a displaceable substituent. Without wishing to be bound by theory, it is thought that one or more instances of A can be displaced from Ni by the ligand to form the Ni-ligand complex. Without wishing to be bound by theory, it is thought that one or more instances of group A are displaced by a complexation reaction between the Ni precursor and the ligand to form the Ni-ligand complex. Each instance of A in general formula (i) may be the same or different. Examples for A include halogen atoms and monovalent organic groups. The monovalent organic group may be a monovalent hydrocarbon group or a monovalent heteroatom containing group.
  • the monovalent heteroatom containing group is exemplified by amino groups, halogenated hydrocarbon groups, silazane groups, carboxylate groups, carboxylic ester groups, carbonyl groups, hydrocarbonoxy groups, sulfonate ester groups, sulfonylimide groups, acetate groups, and cyano groups.
  • halogen atoms for A in general formula (i) include Br, CI, or I.
  • Examples of monovalent halogenated hydrocarbon groups for A include haloalkyl groups, e.g., fluorinated alkyl groups such as CF3, fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3,3,3- trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3- heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl; and chlorinated alkyl groups such as chloromethyl and 3-chloropropyl; halogenated carbocyclic groups such as fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3- difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-
  • Examples of monovalent hydrocarbon groups for A in general formula (i) include, but are not limited to, alkyl, alkenyl, carbocyclic, aryl, and aralkyl.
  • Alkyl groups are exemplified by Me, Et, Pr, Bu, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, dodecyl, undecyl, and octadecyl.
  • Alkenyl groups are exemplified by Vi, allyl, propenyl, and Hex.
  • Carbocyclic groups are exemplified by saturated carbocyclic groups, e.g., cycloalkyl such as cyclopentyl and cyclohexyl, or unsaturated carbocyclic groups, e.g., cycloalkenyl such as cyclopentadienyl, cyclohexenyl, or cyclooctadienyl.
  • Aryl groups are exemplified by Ph, tolyl, xylyl, mesityl, and naphthyl.
  • Aralkyl groups are exemplified by benzyl and 2- phenylethyl.
  • Examples of amino groups for A in general formula (i) have formula -NA'2, where each A' is independently a hydrogen atom or a monovalent hydrocarbon group.
  • Exemplary monovalent hydrocarbon groups for A' include, but are not limited to, alkyl such as Me, Et, Pr, Bu, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, dodecyl, undecyl, and octadecyl; alkenyl such as vinyl, allyl, propenyl, and Hex; carbocyclic groups exemplified by saturated carbocyclic groups, e.g., cycloalkyl such as cyclopentyl and cyclohexyl, or unsaturated carbocyclic groups such as cyclopentadienyl or cyclooctadienyl; aryl such as Ph, tolyl, xylyl, mes
  • each A in general formula (i) may be a silazane group.
  • each A in general formula (i) may be a carboxylic ester group.
  • suitable carboxylic ester groups for A include, but are not limited to OAc, ethylhexanoate (such as 2-EHA), neodecanoate, octanoate, and stearate.
  • Examples of monovalent hydrocarbonoxy groups for A in general formula (i) may have formula -O-A", where A" is a monovalent hydrocarbon group.
  • Examples of monovalent hydrocarbon groups for A" include, but are not limited to, alkyl such as Me, Et, Pr, Bu, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, dodecyl, undecyl, and octadecyl; alkenyl such as Vi, allyl, propenyl, and Hex; cycloalkyl such as cyclopentyl and cyclohexyl; aryl such as Ph, tolyl, xylyl, and naphthyl; aralkyl such as benzyl or 2-phenylethyl.
  • each A" may be an alkyl group, such as Me, Et, nPr, iPr, nBu, iBu, or tBu.
  • each A" may be an alkyl group, and alternatively each A" may be Et, Pr such as iPr or nPr, or Bu.
  • each A in general formula (i) may be an alkyl group, such as Me, Et, nPr, iPr, nBu, iBu, or tBu.
  • each A may be independently selected from the group consisting of Et, benzyl, mesityl, Ph, NEt2, NMe2, cyclooctadiene, ethoxide, iPr, Bu,
  • the Ni precursor may be a commercially available compound, such as those shown below in Table 1 .
  • the ligand is an organic compound that coordinates with Ni.
  • the monovalent organic groups may be monovalent hydrocarbon groups or monovalent heteroatom containing groups.
  • monovalent hydrocarbon groups include, but are not limited to, alkyl such as Me, Et, Pr, Bu, pentyl, or hexyl; alkenyl such as vinyl, allyl, propenyl, and hexenyl; carbocyclic groups exemplified by saturated carbocyclic groups, e.g., cycloalkyl such as cyclopentyl and cyclohexyl, or unsaturated carbocyclic groups such as cyclopentadienyl or cyclooctadienyl; aryl such as Ph and naphthyl; aralkyi such as benzyl, tolyl, xylyl, mesityl, or 2-phenylethyl.
  • Examples of monovalent heteroatom containing groups in the general formulae include a halogenated hydrocarbon group or a hydrocarbonoxy group.
  • Examples of monovalent halogenated hydrocarbon groups include haloalkyi groups such as fluorinated alkyl groups, e.g., CF3, fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, and
  • alkyl groups such as chloromethyl.
  • hydrocarbonoxy groups include alkoxy and aralkyloxy.
  • Alkoxy groups are exemplified by OMe, OEt, OPr, and OBu; alternatively OMe.
  • Aralkyloxy groups are exemplified by phenylmethoxy and phenylethoxy.
  • the monovalent heteroatom containing group may be an aryl group or an aralkyi group having one or more substituents bonded to a carbon atom in the ring, where one or more of the substituents contains a heteroatom, e.g., aralkyloxy described above, or groups such as , where the denotes a point of attachment
  • the ligand may have general formula (ii) :
  • subscript x is an integer from 0 to 1 depending on the valency of Q 1 .
  • Q 1 is selected from oxygen, sulphur, nitrogen and phosphorus.
  • a 1 , A 3 , A 4 , A 5 , and A 6 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A 6 is not chlorobenzene.
  • a 2 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group .
  • a 2 and A 3 may bond together to form a ring structure.
  • a 3 and A 4 may bond together to form a ring structure.
  • a 4 and A 5 may bond together to form a ring structure.
  • a 5 and A 5 may bond together to form a ring structure.
  • a 6 may bond together to form a ring structure.
  • Such a ring structure is fused to the pyridine ring in general formula (ii).
  • Examples of ligands of general formula (ii) include 483, 484, 486, 488, 510, 512, 777, 785, 788, 799, 805, 819, 2363, 6269, 8838, 8842, 8856, 8945, and 8946 in Table 2.
  • the ligand may have general formula
  • Q 2 is oxygen or sulphur.
  • a 7 , A 8 , A 9 , A 1 0 , and A 1 2 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group.
  • a 1 1 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that A 1 1 is not benzyl.
  • a 7 and A 8 may combine to form a ring structure.
  • a 8 and A 9 may combine to form a ring structure.
  • a 9 and A 1 0 may combine to form a ring structure.
  • a 1 1 and A 1 2 may combine to form a ring structure.
  • Examples of ligands of general formula (iii) include 604, 2920, 2921 , 6886, 7282, 7377, and 10364 in Table 2.
  • the ligand may have general formula (iv) :
  • subscript x is an integer from 0 to 1 depending on the valency of Q 3 .
  • Q 3 is selected from oxygen, sulphur, and nitrogen.
  • a 5 , A 6 , A 7 , A 8 , A 20 , and A 21 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group.
  • each A 1 9 is independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A19 does not contain diphenylphosphine.
  • a 20 and A 21 can be bonded together to form a ring structure.
  • a 1 9 and A 1 8 can be bonded together to form a ring structure.
  • a 1 8 and A 1 7 can be bonded together to form a ring structure.
  • a 1 7 and A 1 6 can be bonded together to form a ring structure.
  • a 1 7 and A 1 6 can be bonded together to form a ring structure.
  • a 1 6 and A 1 5 can be bonded together to form a ring structure.
  • ligands of general formula (iv) include 755, 1430, 1483, 1832, 2072, 2915, 2927, 3472, 3586, 3746, 3749, 4098, 41 17, 5479, 6870, 7124, 7471 , 7496, 10132, and 10218 in Table 2.
  • the ligand may have general formula (v):
  • subscript x is an integer from 0 to 1 depending on the valency of Q 4 and whether Q 4 to A 29 is a single or double bond denoted by the dashed line.
  • Subscript y is an integer from 0 to 1 depending on the valency of Q 5 , and whether Q 5 to A 31 is a single or double bond denoted by the dashed line.
  • Q 4 and Q 5 are each independently selected from N, O, P, and S.
  • a 25 , A 26 , A 27 , A 28 , A 29 , A 30 , A 31 , and A 32 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group.
  • a 29 and A 25 may be bonded together to form a ring structure.
  • a 2 ⁇ and A 2 ⁇ may be bonded together to form a ring structure.
  • a 2 ⁇ and A 27 may be bonded together to form a ring structure.
  • a 27 and A 28 may be bonded together to form a ring structure.
  • a 28 and A 32 may be bonded together to form a ring structure.
  • a 29 and A 3 ⁇ may be bonded together to form a ring structure, with the proviso that the ring structure formed is not pyrrole.
  • A31 and A ⁇ 2 may be bonded together to form a ring structure, with the proviso that the ring structure formed is not pyrrole.
  • Examples of ligands of general formula (v) include 165, 788, 799, 805, 819, 1 1 16, 1 125, 1214, 1547, 3544, 3547, 4151 , 4202, 7639, and 8749 in Table 2.
  • the ligand may have general formula (vi):
  • subscript x is an integer from 0 to 1 depending on the valency of Q 8 .
  • Q 8 is selected from N, O, P, and S.
  • a 45 , A 46 , A 47 , A 49 , A 50 , A 51 , and A 52 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that when Q 8 is sulphur then A 4 5 is not benzene.
  • a 48 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group.
  • a 4 ⁇ and A ⁇ 2 may combine to form a ring structure.
  • a ⁇ 2 and may combine to form a ring structure.
  • a ⁇ 1 and A ⁇ 0 may combine to form a ring structure.
  • a ⁇ O and A 49 may combine to form a ring structure.
  • a 4 ⁇ and A 4 ⁇ may combine to form a ring structure.
  • Examples of ligands of general formula (vi) include 635, 1249, 1888, 2061 , 2062, 2075, 2272, 3096, 3191 , 4202, 4990, 5177, 6253, 6322, 6340, 6372, 7124, and 7534.
  • the ligand may have general formula (vii):
  • subscript x is an integer from 0 to 1 depending on the valency of Q 1 °.
  • Q 1 0 is selected from N, O, P, and S.
  • a dashed line indicates single or double bond.
  • a ⁇ 6 and A ⁇ 7 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group.
  • a ⁇ 8 and A ⁇ 5 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group.
  • a ⁇ 6 and A ⁇ 7 may combine to form a ring structure.
  • a ⁇ 5 and A ⁇ 6 may combine to form a ring structure.
  • Examples of ligands of general formula (vii) include ligands 732, 734, 735, 1936, 2956, 6417, 9042, and 10267 in Table 2.
  • ligand may have general formula (viii) :
  • subscript x is an integer from 0 to 1 depending on the valency of Q 1 1 .
  • Subscript y is an integer from 0 to 1 depending on the valency of Q 1 2 .
  • Q 1 1 and Q 1 2 are each independently selected from N, O, P, and S with the proviso that if Q 1 1 or Q 1 2 are nitrogen then they are not imine nitrogen. Dashed lines represent either single or double bonds.
  • a ⁇ O, A ⁇ 1 , A ⁇ and A66 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group.
  • each A 62 , each A 63 , and each A 64 are independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group.
  • a ⁇ O and may be bonded together to form a ring structure.
  • a ⁇ 1 and A ⁇ 2 may be bonded together to form a ring structure.
  • a ⁇ 2 and A 63 may be bonded together to form a ring structure.
  • A63 and A ⁇ 4 may be bonded together to form a ring structure.
  • a ⁇ 4 and A65 may be bonded together to form a ring structure.
  • A65 and A66 may be bonded together to form a ring structure.
  • A63 and A ⁇ 1 may be bonded together to form a ring structure.
  • Examples of ligands of general formula (viii) include 748, 1214, 1769, 3499, 3547, 3746, 3749, 6322, 6372, 7534, 8881 , 8977, 9042, and 9072 in Table 2.
  • the ligand may have general formula (ix) :
  • subscript x is an integer from 0 to 1 depending on the valency of Q 1 7 .
  • Q 1 7 is selected from N, O, P, and S.
  • Q 1 7 may alternatively be carbon with the proviso that when Q17 is carbon, the carbon forms a carbonyl bond with A 81 and a hydroxyl group with A 80 (for example ligand 2816).
  • Q 1 8 is selected from O and S.
  • Q 1 9 is selected from hydroxyl and thiol.
  • a 82 , A 8 ⁇ , A 84 , and A 8 ⁇ are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group.
  • a 8 ⁇ and A 81 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group.
  • a 81 and A 82 may bond together to form a ring structure.
  • a 82 and A 8 ⁇ may bond together to form a ring structure.
  • a 8 ⁇ and A 84 may bond together to form a ring structure.
  • a 84 and A 85 may bond together to form a ring structure.
  • Examples of ligands of general formula (ix) include ligands 2816, 3500, and 3505 in Table 2.
  • the ligand may have general formula (x):
  • subscript x is an integer from 0 to 1 depending on the valency of Q 1 6 .
  • Q 1 6 is selected from N, O, P, and S.
  • Q 1 4 is selected from oxygen and sulphur.
  • Q 1 5 j S selected from hydroxyl and thiol.
  • each A 76 is independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group.
  • a 77 and A 78 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group.
  • a 76 and A 77 may bond together to form a ring structure.
  • a 77 and A 78 may bond together to form a ring structure.
  • Examples of ligands of general formula (x) include 2363, 2806, and 4226.
  • the ligand may have general formula (xi),
  • subscript x is an integer from 0 to 2 depending on the valency of Q 50 .
  • Q 50 is selected from N and C.
  • Subscripts y and z are each independently an integer from 0 to 1 depending on the valency of the N that A 90 and A 88 are attached to, respectively.
  • the dashed lines indicate single or double bonds.
  • the two nitrogen atoms may be positively charged with a balancing negatively charged anion, alternatively chlorine or boron tetrafluoride
  • a 86 and each A 89 are each independently selected from a monovalent organic group, hydrogen, or an inorganic heteroatom containing group, with the proviso that A 86 may not contain thiol or phenyl di-isopropyl.
  • a 87 A 88 , A 90 , and A 91 are each independently selected from a monovalent organic group, hydrogen, or an inorganic heteroatom containing group.
  • a 88 and A 90 may be bonded together to form a ring structure.
  • a 87 and A 88 may be bonded together to form a ring structure.
  • a 87 and A 86 may be bonded together to form a ring structure.
  • a 86 and A 91 may be bonded together to form a ring structure.
  • a 86 and A 91 may be bonded together to form a ring structure.
  • a 91 and A 90 may be bonded together to form a ring structure.
  • ligands of general formula (xi) include 4226, 6253, 6340, 8500, 8538, 8749, 8881 , 8977, 9042, 10374, 10376, 10377, 10379, 10380, 10381 , 10390, 10450, 10451 , 10452, 10454, 10455, 10456, and 10457 in Table 2.
  • the ligand may have general formula (xii)
  • subscript x is an integer from 1 to 5.
  • Q 20 is selected from N and P. Dashed lines indicate a single or double bond.
  • a 90 , A 9 , A 92 , A 93 A 94 , and A 95 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that when Q 20 is nitrogen and A95 is hydrogen then A 9 ⁇ and A 91 are not cyclohexyl, and with the proviso that A90 and A91 are not be di(tert-butyl) phenol.
  • a 90 and A 91 may be bonded together to form a ring structure, with the proviso that when the ring is a phosphalane ring, then A92 and A93 form a phenyl group.
  • a 91 and A 92 may be bonded together to form a ring structure.
  • a 92 and A 93 may be bonded together to form a ring structure with the proviso that when Q 2 ⁇ is nitrogen then the ring structure is not indene.
  • a 93 and A 94 may be bonded together to form a ring structure with the proviso that when Q 20 is nitrogen then there are no other hetero-atoms in the ring structure with Q 2 ⁇ .
  • a 94 and A 95 may be bonded together to form a ring structure.
  • ligands of general formula (xii) include ligands 10383, 10384, 10385, 10386, 10387, 10389, 10391 , 10392, 10394, 10397, 10398, 10399, 10400, 10401 , 10404, 10407, and 10447 in Table 2.
  • subscript x is an integer from 0 to 1 depending on the valency of Q 21 .
  • Q 21 is selected from N, O, P, and S.
  • A96, A97, A98, A99, A 1 00, A 01 , A 1 02, A103, a 104, A 1 05, A 1 06 j A " ! 07, a nd A108 are eacn independently selected from a monovalent organic group, hydrogen, a halogen, and an inorganic heteroatom containing group.
  • A96 and A97 may bond together to form a ring structure.
  • a 1 06 a nd A 1 05 ma y bond together to form a ring structure.
  • a 1 05 and A 1 °4 ma y bond together to form a ring structure, with the proviso that the bridging atom is not N in an amine group.
  • a 1 04 a nd A 1 03 ma y bond together to form a ring structure.
  • a 1 03 a nd A 1 02 ma y bond together to form a ring structure.
  • a 1 °2 and A 1 °1 may bond together to form a ring structure.
  • Examples of ligands of general formula (xiii) include 10403, 10405, 10406, and 10446 in Table 1 .
  • subscripts x and y are each independently an integer from 0 to 5.
  • A11 1 , A110, and A1 1 2 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group.
  • Examples of ligands of general formula (xiv) include 3179 in Table 2.
  • the ligand may have general formula (xv):
  • Q 2 2 and Q 23 are each independently selected from oxygen and sulphur.
  • A1 15, A1 16, A117, and A118 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group.
  • a 1 1 6 and A 1 1 5 may combine to form a ring structure.
  • a 1 1 8 and A 1 1 9 may combine to form a ring structure. Examples of ligands of general formula
  • (xv) include ligands 4570 and 8768 in Table 2.
  • Q 24 and Q 25 are each independently selected from O and S.
  • Subscript z is an integer from 0 to 1 .
  • each A 1 2 ⁇ is independently selected from a monovalent organic group, hydrogen, halogen, and inorganic heteroatom containing group.
  • a 1 21 and A 1 22 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group.
  • Examples of ligands of general formula (xvi) include 4548 and 6510 in Table 2.
  • the ligand may have general formula (xvii):
  • Q 26 is selected from O and S.
  • Q 27 is selected from N and C.
  • Subscript x is an integer from 0 to 4.
  • a 5 , A 6 , A 7 , A 8 , and A 30 are each independently selected from a monovalent organic group, hydrogen, a halogen, or an inorganic heteroatom containing group.
  • a 1 29 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group, with the proviso that A 1 28 and A 129 may combine to form a ring structure.
  • Examples of ligands of general formula (xvii) include 10441 , 10444, and 10445 in Table 2. [0107] Alternatively, the ligand may have general formula (xviii):
  • a 1 34 are eac h independently selected from a monovalent organic group, hydrogen, a halogen, or an inorganic heteroatom containing group.
  • a 1 31 and A 1 35 are independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group.
  • Examples of ligands of general formula (xviii) include 10453 in Table 2.
  • the ligand may have general formula (xix):
  • each A 1 41 , each A 1 42 , each A 1 4 3, and each A 1 44 are independently selected from a monovalent organic group, hydrogen, halogen, or inorganic group.
  • a 1 36 j A 1 3 j A 1 39 j anc : A 14 0 are independently selected from a monovalent organic group, hydrogen, or an inorganic group.
  • Examples of ligands of general formula (xix) include 10150 in Table 2.
  • ligand used to prepare ingredient (A) may be a ligand selected from the group consisting of the ligands in Table 2
  • Ingredient (A) may be prepared by a method comprising combining a ligand and a Ni precursor, described above.
  • the method may optionally further comprise a step of dissolving either the Ni precursor, or the ligand, or both, in a solvent before combining the Ni precursor and the ligand.
  • Suitable solvents are exemplified by those described below for ingredient (S).
  • the ligand may be dissolved in a solvent in a container, and the solvent may thereafter be removed before adding the Ni precursor to the container with the ligand.
  • the amounts of ligand and Ni precursor are selected such that the mole ratio of ligand to Ni precursor (Metal: Ligand Ratio) may range from 10:1 to 1 :10, alternatively 2:1 to 1 :2, alternatively 1 :1 to 1 :4, and alternatively 1 :1 to 1 :2.
  • Method: Ligand Ratio Metal: Ligand Ratio
  • Combining the Ni precursor and the ligand may be performed by any convenient means, such as mixing them together in or shaking the container.
  • Reacting the Ni precursor and ligand may be performed by under any convenient conditions such as allowing the Ni precursor and ligand prepared as described above to react at -80 °C to 200 °C, alternatively room temperature (RT) of 25 ⁇ for a period of time, by heating, or a combination thereof. Heating may be performed at, for example greater than 25 °C to 200 °C, alternatively greater than 25 °C to 75 °C. Heating may be performed by any convenient means, such as via a heating mantle, heating coil, or placing the container in an oven.
  • the complexation reaction temperature depends on various factors including the reactivities of the specific Ni precursor and ligand selected and the Metal : Ligand Ratio, however, temperature may range from 25 °C to 200 °C, alternatively 25 °C to 75 °C.
  • Complexation reaction time depends on various factors including the reaction temperature selected, however, complexation reaction time may typically range from 1 second (s) to 48 hours (h), alternatively 1 minute (min) to 30 hours (h), and alternatively 45 min to 15 h.
  • the ligand and Ni precursor may be combined and heated sequentially. Alternatively, the ligand and Ni precursor may be combined and heated concurrently.
  • the method of preparing the catalytically active reaction product of ingredient (A) may further comprise activating the reaction product prepared as described above.
  • Activating the reaction product can be performed by reducing the formal oxidation state of the metal atom in the Ni-ligand complex by combining the reaction product described above with a reducing agent.
  • reducing agents include an alkalimetal amalgam ; hydrogen, a metal hydride such as lithium aluminum hydride (UAIH4) or sodium naphthalenide; a silyl hydride (which may be in addition to, or instead of, all or a portion of a silane crosslinker, described below); or a metal borohydride such as sodium triethylborohydride (NaEt3BH), lithium
  • LiEt ⁇ BH triethylborohydride
  • NaBH ⁇ sodium borohydride
  • Suitable reducing agents include those described in Chem. Rev. 1996, 96, 877-910.
  • reaction product described above can be activated by a process comprising combining the reaction product described above with an ionic activator.
  • ionic activators for use in this process include carboranes, such as
  • metal borates such as lithium tetrakis(pentafluorophenyl)borate (LiBArF), lithium tetrakis(3,5- trifluoromethyl)phenylborate, sodium tetrakis(3,5-trifluoromethyl)phenylborate, or a mixture thereof.
  • the reduction product described above can be activated by a method comprising combining the reaction product described above with a neutral activator.
  • neutral activators for use in this method include tris(pentafluorophenyl)borane and tris(pentafluorophenyl)allane.
  • the method of preparing the catalytically active reaction product of ingredient (A) may optionally further comprise adding a solvent after the reaction. Suitable solvents are exemplified by those described below for ingredient (S). Alternatively, the method may optionally further comprise removing a reaction by-product and/or the solvent, if the solvent is present ( e.g., used to facilitate combination of the Ni precursor and the ligand before or during the complexation reaction.
  • By-products include, for example, H-A (where A is as defined above in general formula (i)) or any species resulting from reacting a displaceable substituent off the Ni precursor when the ligand reacts with the Ni precursor.
  • By-products may be removed by any convenient means, such as stripping or distillation, with heating or under vacuum, and/or filtration, crystallization, or a combination thereof.
  • the resulting isolated Ni-ligand complex may be used as the catalytically active reaction product of ingredient (A).
  • the reaction by-products are not removed before using the catalytically active reaction product as ingredient (A).
  • the ligand and Ni precursor may be reacted as described above, with or without solvent removal, and with or without activation, and the resulting reaction product (comprising the Ni-ligand complex and the reaction by-product and optionally a solvent or diluent) may be used as ingredient (A).
  • a by-product may act as a hydrosilylation reaction catalyst, or as a co-catalyst or an activator, in addition to the Ni- ligand complex. Therefore, the reaction product may catalyze a hydrosilylation reaction.
  • the composition may contain one single catalyst.
  • the composition may comprise two or more catalysts described above as ingredient (A), where the two or more catalysts differ in at least one property such as selection of ligand, selection of precursor, Metal: Ligand Ratio, and definitions for group A in general formula (i).
  • the composition may be free of platinum catalysts.
  • the composition may be free of conventional metal catalysts.
  • the composition may be free of any Ni compound that would catalyze the hydrosilylation reaction of the unsaturated groups on ingredient (B) other than the ingredient (A).
  • the composition may be free of hydrosilylation reaction catalysts other than ingredient (A).
  • the composition may be free of any ingredient that would catalyze the hydrosilylation reaction of the unsaturated groups on ingredient (B) other than ingredient (A).
  • Ingredient (A) is present in the composition in a catalytically effective amount.
  • the exact amount depends on various factors including reactivity of ingredient (A), the type and amount of ingredient (B), and the type and amount of any additional ingredient, if present.
  • the amount of ingredient (A) in the composition may range from 1 part per million (ppm) to 5 %, alternatively 0.1 % to 2 %, and alternatively 1 ppm to 1 %, based on total weight of all ingredients in the composition.
  • Ingredient (B) is an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction.
  • ingredient (B) may have an average of two or more aliphatically unsaturated organic groups per molecule.
  • the aliphatically unsaturated organic groups may be alkenyl exemplified by, but not limited to, vinyl, allyl, propenyl, butenyl, and hexenyl.
  • the unsaturated organic groups may be alkynyl groups exemplified by, but not limited to, ethynyl, propynyl, and butynyl.
  • Ingredient (B) of the composition may be an unsaturated hydrocarbon, where the unsaturated group is capable of reacting via hydrosilylation reaction.
  • Ingredient (B) may be monomeric.
  • suitable aliphatically unsaturated organic compounds for ingredient (B) include, but are not limited to alkenes such as ethylene, propene, 1 -butene, 2-butene, 1 -pentene, 1 -hexene, 1 -heptene; halogenated alkenes, such as allyl chloride; diolefins such as divinylbenzene, butadiene, 1 ,5-hexadiene, and 1 -buten-3-yne;
  • cycloolefins such as cyclohexene and cycloheptene
  • alkynes such as acetylene, propyne, and 1 -hexyne
  • Oxygen-containing aliphatically unsaturated compounds can also be used for ingredient (B), for example, where the unsaturation is ethylenic, such as vinylcyclohexyl epoxide, allyl glycidyl ether, methylvinyl ether, divinylether, phenylvinyl ether, monoallyl ether of ethylene glycol, allyl aldehyde, methylvinyl ketone, phenylvinyl ketone, acrylic acid, methacrylic acid, methyl acrylate, allyl acrylate, methyl methacrylate, allyl methacrylate, vinylacetic acid, vinyl acetate, and linolenic acid.
  • ethylenic such as vinylcyclohexyl epoxide, allyl glycidyl ether, methylvinyl ether, divinylether, phenylvinyl ether, monoallyl ether of ethylene glycol,
  • Heterocyclic compounds containing aliphatic unsaturation in the ring are also suitable as ingredient (B).
  • Unsaturated compounds containing nitrogen substituents such as acrylonitrile, N-vinylpyrrolidone, alkyl cyanide, nitroethylene are also suitable as ingredient (B).
  • ingredient (B) of the composition comprise a polymer.
  • Ingredient (B) may comprise a base polymer having an average of one or more aliphatically unsaturated organic groups, capable of undergoing a hydrosilylation reaction, per molecule.
  • Ingredient (B) may comprise a polymer (e.g., copolymers or terpolymers) of the various compounds described above, provided there is at least one aliphatic unsaturation capable of undergoing a hydrosilylation reaction.
  • a polymer e.g., copolymers or terpolymers
  • examples include polymers derived from olefinic monomers having 2 to 20 carbon atoms and dienes having 4 to 20 carbon atoms; polymers of monoolefin, isomonoolefin and vinyl aromatic monomers, such as monoolefins having 2 to 20 carbon groups, isomonoolefins having 4 to 20 carbon groups, and vinyl aromatic monomers including styrene, para-alkylstyrene, para-methylstyrene.
  • the compounds can be poly(dienes).
  • polymers derived from dienes usually contain unsaturated ethylenic units on backbone or side-chains.
  • Representative examples include polybutadiene, polyisoprene, polybutenylene, poly(alkyl-butenylene) where alkyl includes alkyl groups having 1 to 20 carbon atoms, poly(phenyl-butenylene), polypentenylene, natural rubber (a form of polyisoprene); and butyl rubber (copolymer of isobutylene and isoprene).
  • ingredient (B) may comprise a halogenated olefin polymer having aliphatic unsaturation.
  • a halogenated olefin polymer having aliphatic unsaturation include polymers resulting from the bromination of a copolymer of isomonoolefin with para-methylstyrene to introduce benzylic halogen, halogenated polybutadienes, halogenated polyisobutylene, poly(2-chloro-1 ,3-butadiene),
  • ingredient (B) may comprise polymers containing other compounds described above such as vinyl ether groups, acrylate groups, methyacrylate groups, and epoxy-functional groups.
  • ingredient (B) may comprise a silane having aliphatic unsaturation.
  • the silane may have a general formula of R 35 xxSiR 36 (4 -xx ) where subscript xx is an integer from 1 to 4, alternatively 1 to 3, and alternatively 1 .
  • R 35 is an aliphatically unsaturaged organic group, and R 36 is selected from H, a halogen atom , and aa monovalent organic group.
  • ingredient (B) may comprise a silicon containing base polymer having a linear, branched, cyclic, or resinous structure having aliphatic unsaturation.
  • the base polymer may have a linear and/or branched structure.
  • the base polymer may have a resinous structure.
  • the base polymer may be a homopolymer or a copolymer.
  • Ingredient (B) may be one base polymer.
  • ingredient (B) may comprise two or more base polymers differing in at least one of the following properties: structure, viscosity, average molecular weight, siloxane units, and sequence.
  • the aliphatically unsaturated organic groups in the base polymer may be located at terminal, pendant, or both terminal and pendant positions.
  • the remaining silicon-bonded organic groups in the base polymer for ingredient (B) may be monovalent organic groups free of aliphatic unsaturation.
  • monovalent hydrocarbon groups include, but are not limited to, alkyl such as Me, Et, Pr, Bu, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl; cycloalkyl such as cyclopentyl and cyclohexyl; aryl such as Ph, tolyl, xylyl, and naphthyl; and aralkyl such as benzyl, 1 -phenylethyl and 2-phenylethyl.
  • monovalent halogenated hydrocarbon groups include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl groups; fluorinated alkyl groups such as fluoromethyl, 2- fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl,
  • Examples of other monovalent organic groups include, but are not limited to, hydrocarbon groups substituted with oxygen atoms such as glycidoxyalkyi, and hydrocarbon groups substituted with nitrogen atoms such as aminoalkyl and cyano-functional groups such as cyanoethyl and cyanopropyl.
  • Ingredient (B) may comprise a polydiorganosiloxane of
  • each R 1 is independently a hydrogen atom or a monovalent organic group free of aliphatic unsaturation and each R 2 is independently an aliphatically unsaturated organic group, exemplified by those described above.
  • Subscript a may be 0 or a positive number.
  • subscript a has an average value of at least 2.
  • subscript a may have a value ranging from 2 to 2000.
  • Subscript b may be 0 or a positive number.
  • subscript b may have an average value ranging from 0 to 2000.
  • Subscript c may be 0 or a positive number.
  • subscript c may have an average value ranging from 0 to 2000.
  • Subscript d has an average value of at least 2. Alternatively subscript d may have an average value ranging from 2 to 2000.
  • Suitable monovalent organic groups for R 1 are as described above for ingredient (B).
  • each R 1 is a monovalent hydrocarbon group exemplified by alkyl such as Me and aryl such as Ph.
  • Each R 2 is independently an aliphatically unsaturated monovalent organic group as described above for ingredient (B).
  • R 2 is exemplified by alkenyl groups such as vinyl, allyl, butenyl, and hexenyl; and alkynyl groups such as ethynyl and propynyl.
  • Ingredient (B) may comprise a polydiorganosiloxane such as
  • (B) may further comprise a resin such as an MQ resin consisting essentially of R 3 3SiO-
  • a resin such as an MQ resin consisting essentially of R 3 3SiO-
  • examples of monovalent organic groups for R 3 include, but are not limited to, monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups.
  • the resin may contain an average of 3 to 30 mole percent of aliphatically unsaturated organic groups, alternatively 0.1 to 30 mole percent, alternatively 0.1 to 5 mole percent, alternatively 3 to 100 mole percent.
  • the aliphatically unsaturated organic groups may be alkenyl groups, alkynyl groups, or a combination thereof.
  • the mole percent of aliphatically unsaturated organic groups in the resin is the ratio of the number of moles of unsaturated group-containing siloxane units in the resin to the total number of moles of siloxane units in the resin, multiplied by 100.
  • resin may be prepared by treating a resin copolymer produced by the silica hydrosol capping process of Daudt, et al. with at least an alkenyl-containing endblocking reagent.
  • the method of Daudt et ai is disclosed in U.S. Patent 2,676,182.
  • the method of Daudt, et al. involves reacting a silica hydrosol under acidic conditions with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or mixtures thereof, and recovering a copolymer having M- units and Q-units.
  • a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or mixtures thereof.
  • the resulting copolymers generally contain from 2 to 5 percent by weight of hydroxyl groups.
  • the resin which typically contains less than 2 % of silicon-bonded hydroxyl groups, may be prepared by reacting the product of Daudt, et al. with an unsaturated organic group-containing endblocking agent and an endblocking agent free of aliphatic unsaturation, in an amount sufficient to provide from 3 to 30 mole percent of unsaturated organic groups in the final product.
  • endblocking agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable endblocking agents are known in the art and exemplified in U.S. Patents 4,584,355; 4,591 ,622; and 4,585,836. A single endblocking agent or a mixture of such agents may be used to prepare the resin.
  • ingredient (B) may comprise a silicon containing base polymer other than the polyorganosiloxanes described above.
  • other compounds suitable for ingredient (B) include silazanes and/or polymeric materials containing silicon atoms joined together by hydrocarbyl groups such as alkylene or polyalkylene groups or arylene groups.
  • the silicon-modified organic compounds useful as ingredient (B) include organic polymers having at least one silicon atom attached as a silane or a siloxane segment.
  • the silicon-containing units can contain aliphatic unsaturation and can be attached at the terminal and/or pendant positions on the organic polymer chain or as a copolymer.
  • silicon-modified organic polymers for ingredient (B) are exemplified by, but not limited to alkenylsiloxy-functional polymers such as vinylsiloxy-, allylsiloxy-, and hexenylsiloxy- organic polymers and siloxane-organic block copolymers.
  • alkenylsiloxy-functional polymers such as vinylsiloxy-, allylsiloxy-, and hexenylsiloxy- organic polymers and siloxane-organic block copolymers.
  • silane-modified organic polymers are silylated polymers derived from olefins
  • isomonoolefin dienes, ethylene or propylene oxides, and vinyl aromatic monomers having 2 to 20 carbon atoms such as the silane-grafted copolymers of isomonoolefin and vinyl aromatic monomers.
  • silicon-modified organic polymers described by above include vinylsiloxy-terminated or hexenylsiloxy-terminated poly(dimethylsiloxane/hydrocarbyl) copolymers, vinylsiloxy-terminated or hexenylsiloxy-terminated
  • poly(dimethylsiloxane/polyoxyalkylene) block copolymers alkenyloxydimethylsiloxy- terminated polyisobutylene and alkenyloxydimethylsiloxy-terminated
  • polydimethylsiloxane/polyisobutylene block copolymers examples include polydimethylsiloxane/polyisobutylene block copolymers.
  • suitable compounds for ingredient (B) may be found, for example, in WO 2003/093369.
  • the amount of ingredient (B) in the composition depends on various factors including the desired form of the reaction product of the composition, the quantity and hydrosilylation reactivity of the aliphatically unsaturated groups of ingredient (B), the type and amount of ingredient (A), and the content of silicon bonded hydrogen atoms of, ingredient (B) and/or ingredient (C). However, the amount of ingredient (B) may range from 0.1 % to 99.9 % based on the weight of all ingredients in the composition.
  • Ingredient (C) in the composition is a SiH functional compound, i.e., a compound having an average, per molecule, of one or more silicon bonded hydrogen atoms.
  • Ingredient (C) may comprise a silane and/or an organohydrogensilicon compound.
  • ingredient (C) may have an average, per molecule, of at least two silicon- bonded hydrogen atoms.
  • the amount of ingredient (C) in the composition depends on various factors including the SiH content of ingredient (C), the unsaturated group content of ingredient (B), and the properties of the reaction product of the composition desired, however, the amount of ingredient (C) may be sufficient to provide a molar ratio of SiH groups in ingredient (C) to aliphatically unsaturated organic groups in ingredient (B) (commonly referred to as the SiH:Vi ratio) ranging from 0.3:1 to 5:1 , alternatively 0.1 :10 to 10:1.
  • Ingredient (C) can have a monomeric or polymeric structure.
  • ingredient (C) When ingredient (C) has a polymeric structure, the polymeric structure may be linear, branched, cyclic, or resinous structure. When ingredient (C) is polymeric, then ingredient (C) can be a homopolymer or a copolymer. The silicon-bonded hydrogen atoms in ingredient (C) can be located at terminal, pendant, or at both terminal and pendant positions. Ingredient (C) may be one SiH functional compound. Alternatively, ingredient (C) may comprise a combination of two or more SiH functional compounds. Ingredient (C) may be two or more organohydrogenpolysiloxanes that differ in at least one of the following properties:
  • Ingredient (C) may comprise a silane of formula R 4 e SiHf, where subscript e is 0,
  • each R 4 is independently a halogen atom or a monovalent organic group. Suitable halogen atoms for
  • R 4 are exemplified by chlorine, fluorine, bromine, and iodine; alternatively chlorine.
  • Suitable monovalent organic groups for R 4 include, but are not limited to, monovalent hydrocarbon and monovalent halogenated hydrocarbon groups.
  • Monovalent hydrocarbon groups include, but are not limited to, alkyl such Me, Et, Pr, Bu, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl; cycloalkyi such as cyclopentyl and cyclohexyl; aryl such as Ph, tolyl, xylyl, and naphthyl; and aralkyl such as benzyl, 1 -phenylethyl and 2- phenylethyl.
  • Examples of monovalent halogenated hydrocarbon groups include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl groups; fluorinated alkyl groups such as fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4- trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3- nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl; chlorinated cycloalkyi groups such as 2,2- dichlorocyclopropyl, 2,3-dichlorocyclopentyl; and fluorinated cycloalkyi groups such as 2,2- difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4
  • Examples of other monovalent organic groups include, but are not limited to, hydrocarbon groups substituted with oxygen atoms such as glycidoxyalkyl, and alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy; and hydrocarbon groups substituted with nitrogen atoms such as aminoalkyl and cyano-functional groups such as cyanoethyl and cyanopropyl.
  • the organohydrogensilicon compound of ingredient (C) may comprise a polyorganohydrogensiloxane comprising siloxane units including, but not limited to, HR 5 2 SiO-
  • each R 5 is independently selected from the monovalent organic groups free of aliphatic unsaturation described above.
  • Ingredient (C) may comprise a polyorganohydrogensiloxane of
  • subscript g has an average value ranging from 0 to 2000
  • subscript h has an average value ranging from 2 to 2000
  • subscript i has an average value ranging from 0 to 2000
  • subscript j has an average value ranging from 0 to 2000.
  • Each R 5 is independently a monovalent organic group, as described above.
  • organohalosilanes are well known in the art. Methods of preparing
  • organohydrogenpolysiloxane resins suitable for use as ingredient (C) are also well known as exemplified in U.S. Patents 5,310,843; 4,370,358; and 4,707,531 .
  • the organohydrogensilicon compound of ingredient (C) may com rise a compound of formula (V) :
  • each R 2 9 is independently selected from a hydrogen atom and a monovalent organic group comprising 1 to 20 member atoms
  • subscript k is an integer with a value ranging from 4- 0 to 18
  • subscript m is an integer with a value ranging from 0 2 to 19
  • k + m is an integer with a value ranging from 3 to 20, alternatively 3 to 40.
  • Each R 30 is independently selected from a monovalent organic group a halogen atom or a siloxane unit as described in the sections above.
  • each R 30 is a functional group independently selected from a halogen atom, an ether group, an alkoxy group, an alkoxyether group, an acyl group, an epoxy group, an amino group, a silyl group, or a -Z- R 31 group, where each Z is independently selected from an oxygen atom and a divalent hydrocarbon group comprising 2 to 20 carbon atoms, each R 31 group is independently selected from -BR 29 U R 32 2-u > -Si R 29 v R 32 3 -v , or a group described by formula (VI) : (R 32 3-nR 29 nSi0 1 /2)w(R 32 2-oR 29 oSi0 2 /2)x(R 32 i -p
  • each R 29 is as described above, the sum of
  • each R 32 is a functional group independently selected from a halogen atom , an ether group, an alkoxy group, an alkoxyether group, an acyl group, an epoxy group, an amino group, a silyl group, or a Z-G
  • subscript ee is 1
  • subscript ff is an integer with a value ranging from 0 to 18
  • subscript gg is an integer with a value ranging from 0 to 18
  • ff+gg is an integer with a value ranging from 2 to 20, provided in formula (VII) that one of the R 32 groups is replaced by the Z group bonding the R 31 group to the cyclosiloxane of formula (VII), and provided further if aa+bb+cc+dd>0 then w+x+y+z>0.
  • organohydrogensilicon compounds are commercially available and include, SYL-OFF® SL2 CROSSLINKER and SYL-OFF® SL12 CROSSLINKER, both of which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.
  • SYL-OFF® SL2 CROSSLINKER and SYL-OFF® SL12 CROSSLINKER, both of which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.
  • the organohydrogensilicon compounds described above and methods for their preparation are exemplified in WO2003/093349 and WO2003/093369.
  • organohydrogensilicon compound may have the general formula:
  • R 33 is a hydrogen atom. Suitable monovalent organic groups for R 33 and/or
  • R 34 are exemplified by those groups described above for R 29 .
  • the exact amount of ingredient (C) in the composition depends on various factors including reactivity of ingredient (A), the type and amount of ingredient (B), whether ingredient (B) contains a silicon bonded hydrogen atom, and the type and amount of any additional ingredient (other than ingredient (C)), if present.
  • the amount of ingredient (C) in the composition may range from 0 % to 25 %, alternatively 0.1 % to 15 %, and alternatively 1 % to 5 %, based on total weight of all ingredients in the composition.
  • Ingredient (D) is a spacer.
  • Spacers can comprise organic particles, inorganic particles, or a combination thereof. Spacers can be thermally conductive, electrically conductive, or both. Spacers can have a desired particle size, for example, particle size may range from 25 micrometers ( ⁇ ) to 125 ⁇ . Spacers can comprise monodisperse beads, such as glass or polymer (e.g., polystyrene) beads. Spacers can comprise thermally conductive fillers such as alumina, aluminum nitride, atomized metal powders, boron nitride, copper, and silver.
  • the amount of ingredient (D) depends on various factors including the particle size distribution, pressure to be applied during use of the composition or the cured product prepared therefrom , temperature during use, and desired thickness of the composition or the cured product prepared therefrom .
  • the composition may contain an amount of ingredient (D) ranging from 0.05 % to 2 %, alternatively 0.1 % to 1 %.
  • Ingredient (E) is an extender and/or a plasticizer.
  • An extender comprising a nonfunctional polyorganosiloxane may be used in the composition.
  • the non- functional polyorganosiloxane may comprise difunctional units of the formula R 6 2Si02/2 and terminal units of the formula R 7 3SiR 28 -, where each R ⁇ and each R 7 are
  • R 28 is an oxygen atom or a divalent group linking the silicon atom of the terminal unit with another silicon atom.
  • the divalent linking group for R 28 may be a divalent organic group, a silicone organic group, or a combination of a divalent hydrocarbon group and a divalent siloxane group.
  • each R 28 may be independently selected from an oxygen atom and a divalent hydrocarbon group.
  • each R 28 may be an oxygen atom .
  • each R 28 may be a divalent hydrocarbon group exemplified by an alkylene group such as ethylene, propylene, butylene, or hexylene; an arylene group such as phenylene, or an alkylarylene group such as: .
  • an instance of R 28 may be an oxygen atom while a different instance of R 28 is a divalent hydrocarbon group.
  • Non-functional polyorganosiloxanes are known in the art and are commercially available.
  • Suitable non-functional polyorganosiloxanes are exemplified by, but not limited to, polydimethylsiloxanes.
  • polydimethylsiloxanes include DOW CORN ING® 200 Fluids, which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A. and may have viscosity ranging from 50 cSt to 1 00,000 cSt, alternatively 50 cSt to 50,000 cSt, and alternatively 12,500 cSt to 60,000 cSt.
  • An organic plasticizer may be used in addition to, or instead of, the non-functional polyorganosiloxane extender described above. Organic plasticizers are known in the art and are commercially available.
  • the organic plasticizer may comprise a phthalate, a carboxylate, a carboxylic acid ester, an adipate or a combination thereof.
  • the organic plasticizer may be selected from the group consisting of: bis(2-ethylhexyl) terephthalate; bis(2-ethylhexyl)-1 ,4-benzenedicarboxylate; 2-ethylhexyl methyl-1 ,4-benzenedicarboxylate; 1 ,2 cyclohexanedicarboxylic acid, dinonyl ester, branched and linear; bis(2-propylheptyl) phthalate; diisononyl adipate; and a combination thereof.
  • the organic plasticizer may have an average, per molecule, of at least one group
  • R 8 represents a hydrogen atom or a monovalent organic group.
  • R 8 may represent a branched or linear monovalent hydrocarbon group.
  • the monovalent organic group may be a branched or linear monovalent hydrocarbon group such as an alkyl group of 4 to 15 carbon atoms, alternatively 9 to 12 carbon atoms.
  • Suitable plasticizers may be selected from the group consisting of adipates, carboxylates, phthalates, and a combination thereof.
  • the organic plasticizer may have an average, per molecule, of at least two groups of the formula above bonded to carbon atoms in a cyclic hydrocarbon.
  • T have general formula:
  • group Z represents a cyclic hydrocarbon group having 3 or more carbon atoms, alternatively 3 to 15 carbon atoms.
  • Subscript k may have a value ranging from 1 to
  • Group Z may be saturated or aromatic.
  • Each R 1 0 is independently a hydrogen atom or a branched or linear monovalent organic group.
  • the monovalent organic group for R 9 may be an alkyl group such as Me, Et, or Bu. Alternatively, the monovalent organic group for R 1 0 may be an ester functional group.
  • Each R 9 is independently a branched or linear monovalent hydrocarbon group, such as an alkyl group of 4 to 15 carbon atoms.
  • Suitable organic plasticizers are known in the art and are commercially available.
  • the plasticizer may comprise a phthalate, such as: a dialkyl phthalate such as dibutyl phthalate (EastmanTM DBP Plasticizer), diheptyl phthalate, di(2-ethylhexyl) phthalate, or diisodecyl phthalate (DIDP), bis(2-propylheptyl) phthalate (BASF Palatinol® DPHP) , di(2- ethylhexyl) phthalate (EastmanTM DOP Plasticizer), dimethyl phthalate (EastmanTM DMP Plasticizer); diethyl phthalate (EastmanTM DMP Plasticizer); butyl benzyl phthalate, and bis(2-ethylhexyl) terephthalate (EastmanTM 425 Plasticizer); a dicarboxylate such as Benzyl, C7-C9 linear and branched alkyl esters, 1
  • EastmanTM TEG-EH Plasticizer triacetin
  • nonaromatic dibasic acid esters such as dioctyl adipate, bis(2-ethylhexyl) adipate (EastmanTM DOA Plasticizer and EastmanTM DOA Plasticizer, Kosher), di-2-ethylhexyladipate (BASF Plastomoll® DOA), dioctyl sebacate, dibutyl sebacate and diisodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl recinolate; phosphates such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; process oils; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate; tris(2-ethyl)
  • a polymer plasticizer can be used.
  • the polymer plasticizer include alkenyl polymers obtained by polymerizing vinyl or allyl monomers by means of various methods; polyalkylene glycol esters such as diethylene glycol dibenzoate, triethylene glycol dibenzoate and pentaerythritol ester; polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; polyethers including polyether polyols each having a molecular weight of not less than 500 such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polystyrenes such as polystyrene and poly-alpha- methylstyrene; and polybutadiene, polybutene, polyisobutylene, butad
  • the polyorganosiloxane extenders and organic plasticizers described above for ingredient (E) may be used either each alone or in combinations of two or more thereof.
  • a low molecular weight organic plasticizer and a higher molecular weight polymer plasticizer may be used in combination.
  • the exact amount of ingredient (E) used in the composition will depend on various factors including the desired end use of the composition and the cured product thereof. However, the amount of ingredient (E) may range from 0.1 % to 10 % based on the combined weights of all ingredients in the composition.
  • Ingredient (F) is a filler.
  • the filler may comprise a reinforcing filler, an extending filler, a conductive filler, or a combination thereof.
  • the composition may optionally further comprise ingredient (f 1 ), a reinforcing filler, which when present may be added in an amount ranging from 0.1 % to 95 %, alternatively 1 % to 60 %, based on the weight of the composition.
  • ingredient (f 1 ) depends on various factors including the form of the reaction product of the composition ⁇ e.g., gel or rubber) and whether any other fillers are added.
  • suitable reinforcing fillers include chopped fiber such as chopped KEVLAR®, and/or reinforcing silica fillers such as fume silica, silica aerogel, silica xerogel, and precipitated silica.
  • chopped fiber such as chopped KEVLAR®
  • reinforcing silica fillers such as fume silica, silica aerogel, silica xerogel, and precipitated silica.
  • Fumed silicas are known in the art and commercially available; e.g., fumed silica sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts, U.S.A.
  • the composition may optionally further comprise ingredient (f2) an extending filler in an amount ranging from 0.1 % to 95 %, alternatively 1 % to 60 %, and alternatively 1 % to 20 %, based on the weight of the composition.
  • extending fillers include crushed quartz, aluminum oxide, magnesium oxide, calcium carbonate such as
  • precipitated calcium carbonate zinc oxide, talc, diatomaceous earth, iron oxide, clays, mica, titanium dioxide, zirconia, sand, carbon black, graphite, or a combination thereof.
  • Extending fillers are known in the art and commercially available; such as a ground silica sold under the name MIN-U-SIL by U.S. Silica of Berkeley Springs, WV.
  • Suitable precipitated calcium carbonates included Winnofil® SPM from Solvay and Ultrapflex® and Ultrapf lex® 100 from SMI.
  • the composition may optionally further comprise ingredient (f3) a conductive filler.
  • Ingredient (F) may be both thermally conductive and electrically conductive.
  • ingredient (F) may be thermally conductive and electrically insulating.
  • Ingredient (F) may be selected from the group consisting of aluminum nitride, aluminum oxide, aluminum trihydrate, barium titanate, beryllium oxide, boron nitride, carbon fibers, diamond, graphite, magnesium hydroxide, magnesium oxide, metal particulate, onyx, silicon carbide, tungsten carbide, zinc oxide, and a combination thereof.
  • Ingredient (F) may comprise a metallic filler, an inorganic filler, a meltable filler, or a combination thereof.
  • Metallic fillers include particles of metals and particles of metals having layers on the surfaces of the particles. These layers may be, for example, metal nitride layers or metal oxide layers on the surfaces of the particles. Suitable metallic fillers are exemplified by particles of metals selected from the group consisting of aluminum, copper, gold, nickel, silver, and combinations thereof, and alternatively aluminum. Suitable metallic fillers are further exemplified by particles of the metals listed above having layers on their surfaces selected from the group consisting of aluminum nitride, aluminum oxide, copper oxide, nickel oxide, silver oxide, and combinations thereof. For example, the metallic filler may comprise aluminum particles having aluminum oxide layers on their surfaces.
  • Inorganic conductive fillers are exemplified by onyx; aluminum trihydrate, metal oxides such as aluminum oxide, beryllium oxide, magnesium oxide, and zinc oxide; nitrides such as aluminum nitride and boron nitride; carbides such as silicon carbide and tungsten carbide; and combinations thereof.
  • inorganic conductive fillers are exemplified by aluminum oxide, zinc oxide, and combinations thereof.
  • Meltable fillers may comprise Bi, Ga, In, Sn, or an alloy thereof.
  • the meltable filler may optionally further comprise Ag, Au, Cd, Cu, Pb, Sb, Zn, or a combination thereof.
  • meltable fillers examples include Ga, In-Bi-Sn alloys, Sn-ln-Zn alloys, Sn-ln-Ag alloys, Sn-Ag-Bi alloys, Sn-Bi-Cu-Ag alloys, Sn-Ag-Cu-Sb alloys, Sn-Ag-Cu alloys, Sn-Ag alloys, Sn-Ag-Cu- Zn alloys, and combinations thereof.
  • the meltable filler may have a melting point ranging from 50 2 C to 250 2 C, alternative ⁇ 50 2 C to 225 2 C.
  • the meltable filler may be a eutectic alloy, a non-eutectic alloy, or a pure metal. Meltable fillers are commercially available.
  • meltable fillers may be obtained from Indium Corporation of America, Utica, N.Y. , U.S.A.; Arconium , Buffalo, R.I., U.S.A.; and AIM Solder, Cranston, R.I., U.S.A.
  • Aluminum fillers are commercially available, for example, from Toyal America, Inc. of Naperville, Illinois, U.S.A. and Valimet Inc., of Stockton, California, U.S.A.
  • Silver filler is commercially available from Metalor Technologies U.S.A. Corp. of Attleboro, Massachusetts, U.S.A.
  • Thermally conductive fillers are known in the art and commercially available.
  • CB-A20S and AI-43-Me are aluminum oxide fillers of differing particle sizes commercially available from Showa-Denko, and AA-04, AA-2, and AA18 are aluminum oxide fillers commercially available from Sumitomo Chemical Company.
  • Zinc oxides such as zinc oxides having trademarks KADOX® and XX®, are commercially available from Zinc Corporation of America of Monaca, Pennsylvania, U.S.A.
  • the shape of the filler particles is not specifically restricted, however, rounded or spherical particles may prevent viscosity increase to an undesirable level upon high loading of the filler in the composition.
  • Ingredient (F) may be a single filler or a combination of two or more fillers that differ in at least one property such as particle shape, average particle size, particle size distribution, and type of filler.
  • a combination of fillers such as a first filler having a larger average particle size and a second filler having a smaller average particle size.
  • Use of a first filler having a larger average particle size and a second filler having a smaller average particle size than the first filler may improve packing efficiency and/or may reduce viscosity of the composition as compared to a composition without such a combination of fillers.
  • the average particle size of the filler will depend on various factors including the type of the filler selected for ingredient (F) and the exact amount added to the composition, as well as the end use for the reaction product of the composition. However, the filler may have an average particle size ranging from 0.1 to 80 ⁇ , alternatively 0.1 to 50 ⁇ , and alternatively 0.1 to 10 ⁇ .
  • the amount of ingredient (F) in the composition depends on various factors including the end use selected for the composition and the reaction product of the composition, the type and amount of ingredient (B), and the type and amount of the filler selected for ingredient (F). However, the amount of ingredient (F) may range from 0 vol % to 80 vol %, alternatively 50 vol % to 75 vol %, and alternatively 30 % to 80 %, by volume of the composition. Without wishing to be bound by theory, it is thought that when the amount of filler is greater than 80 vol %, the composition may react to form a reaction product with insufficient dimensional integrity for some applications.
  • the composition may optionally further comprise ingredient (G) a treating agent.
  • ingredient (G) a treating agent.
  • the amount of ingredient (G) will vary depending on factors such as the type of treating agent selected and the type and amount of particulates (such as ingredients (F) and/or (D)) to be treated, and whether the particulates are treated before being added to the composition, or whether the particulates are treated in situ.
  • ingredient (G) may be used in an amount ranging from 0.01 % to 20 %, alternatively 0.1 % to 15 %, and alternatively 0.5 % to 5 %, based on the weight of all ingredients in the composition.
  • Particulates such as the filler, the physical drying agent, certain flame retardants, and/or certain pigments, when present, may optionally be surface treated with ingredient (G). Particulates may be treated with ingredient (G) before being added to the composition, or in situ.
  • Ingredient (G) may comprise an alkoxysilane, an alkoxy-functional oligosiloxane, a cyclic polyorganosiloxane, a hydroxyl-functional oligosiloxane such as a dimethyl siloxane or methyl phenyl siloxane, or a fatty acid.
  • fatty acids include stearates such as calcium stearate.
  • organosilicon filler treating agents that can be used as ingredient (G) include compositions normally used to treat silica fillers such as
  • organochlorosilanes organosiloxanes, organodisilazanes such as hexaalkyl disilazane, and organoalkoxysilanes such as C6H-
  • treating agents include alkylthiols, fatty acids, titanates, titanate coupling agents, zirconate coupling agents, and combinations thereof.
  • ingredient (G) may comprise an alkoxysilane having the formula: R 1 1 m Si(OR 1 2 )(4 -m ) , where subscript m may have a value ranging from 1 to 3, alternatively subscript m is 3.
  • R 1 1 is independently a monovalent organic group, such as a monovalent hydrocarbon group of 1 to 50 carbon atoms, alternatively 8 to 30 carbon atoms, alternatively 8 to 18 carbon atoms.
  • R 1 1 is exemplified by alkyl groups such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; and aromatic groups such as benzyl and phenylethyl.
  • R 1 1 may be saturated or unsaturated, and branched or unbranched. Alternatively, R 1 1 may be saturated and unbranched.
  • Each R 1 2 is independently a saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms.
  • Alkoxysilanes suitable for use as ingredient (G) are exemplified by hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, phenylethyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and combinations thereof.
  • Alkoxy-functional oligosiloxanes may also be used as treating agents.
  • suitable alkoxy-functional oligosiloxanes include those of the formula (V) :
  • each R 1 3 may be an alkyl group.
  • Each R 1 4 may be an unsaturated monovalent hydrocarbon group of 1 to 10 carbon atoms.
  • Each R 1 5 may be an unsaturated monovalent hydrocarbon group having at least 10 carbon atoms.
  • Certain particulates, such as metal fillers may be treated with alkylthiols such as octadecyl mercaptan; fatty acids such as oleic acid and stearic acid; and a combination thereof.
  • alkylthiols such as octadecyl mercaptan
  • fatty acids such as oleic acid and stearic acid
  • Treatment agents for alumina or passivated aluminum nitride may include alkoxysilyl functional alkylmethyl polysiloxanes ⁇ e.g., partial hydrolysis condensate of
  • a group tethered to Si such as R 1 6 in the formula above, is a long chain unsaturated monovalent hydrocarbon or monovalent aromatic-functional hydrocarbon.
  • Each R 1 7 is independently a monovalent hydrocarbon group
  • each R 1 8 is independently a monovalent hydrocarbon group of 1 to 4 carbon atoms.
  • subscript o is 1 , 2, or 3 and subscript p is 0, 1 , or 2, with the proviso that a sum (o + p) is 1 , 2, or 3.
  • alkenyl functional polyorganosiloxanes include, but are not limited to:
  • treating agents include mono-endcapped alkoxy functional polydiorganosiloxanes, i.e., polydiorganosiloxanes having an alkoxy group at one end. Such treating agents are exemplified by the formula:
  • Each R 25 is independently selected from an alkyl group, such as Me, Et, Pr, Bu, hexyl, and octyl; and an alkenyl group, such as Vi, allyl, butenyl, and Hex.
  • Each R 26 is independently an alkyl group such as Me, Et, Pr, Bu, hexyl, and octyl.
  • Each R 27 is independently an alkyl group such as Me, Et, Pr, and Bu.
  • each R 25 , each R 26 , and each R 27 is Me.
  • each R 2 ⁇ is Vi.
  • each R 2 ⁇ and each R 27 is Me.
  • a polyorganosiloxane capable of hydrogen bonding is useful as a treating agent.
  • This strategy to treating surface of a filler takes advantage of multiple hydrogen bonds, either clustered or dispersed or both, as the means to tether the compatibilization moiety to the filler surface.
  • the polyorganosiloxane capable of hydrogen bonding has an average, per molecule, of at least one silicon-bonded group capable of hydrogen bonding.
  • the group may be selected from : an organic group having multiple hydroxyl functionalities or an organic group having at least one amino functional group.
  • the polyorganosiloxane capable of hydrogen bonding means that hydrogen bonding is the primary mode of attachment for the polyorganosiloxane to a filler.
  • the polyorganosiloxane may be incapable of forming covalent bonds with the filler.
  • the polyorganosiloxane capable of hydrogen bonding may be selected from the group consisting of a saccharide- siloxane polymer, an amino-functional polyorganosiloxane, and a combination thereof.
  • the polyorganosiloxane capable of hydrogen bonding may be a saccharide- siloxane polymer.
  • Ingredient (H) is a biocide.
  • the amount of ingredient (H) will vary depending on factors including the type of biocide selected and the benefit desired. However, the amount of ingredient (H) may range from greater than 0 % to 5 % based on the weight of all ingredients in the composition.
  • Ingredient (H) is exemplified by (hi ) a fungicide, (h2) an herbicide, (h3) a pesticide, (h4) an antimicrobial agent, or a combination thereof.
  • Ingredient (hi ) is a fungicide, for example, these include N-substituted benzimidazole carbamate, benzimidazolyl carbamate such as methyl 2- benzimidazolylcarbamate, ethyl 2-benzimidazolylcarbamate, isopropyl 2- benzimidazolylcarbamate, methyl N- ⁇ 2-[1 -(N,N- dimethylcarbamoyl)benzimidazolyl] ⁇ carbamate, methyl N- ⁇ 2-[1 -(N,N-dimethylcarbamoyl)-6- methylbenzimidazolyl] ⁇ carbamate, methyl N- ⁇ 2-[1 -(N,N-dimethylcarbamoyl)-5- methylbenzimidazolyl] ⁇ carbamate, methyl N- ⁇ 2-[1 -(N-methylcarbamoyl)benzimidazolyl] Jcarbamate, methyl N- ⁇ 2-[1
  • Ingredient (h2) is an herbicide
  • suitable herbicides include amide herbicides such as allidochlor /V,/V-diallyl-2-chloroacetamide; CDEA 2-chloro-/V,/V- diethylacetamide; etnipromid (RS)-2-[5-(2,4-dichlorophenoxy)-2-nitrophenoxy]-/V- ethylpropionamide; anilide herbicides such as cisanilide c/ ' s-2,5-dimethylpyrrolidine-1 - carboxanilide; flufenacet 4'-fluoro-/V-isopropyl-2-[5-(trifluoromethyl)-1 ,3,4-thiadiazol-2- yloxy]acetanilide; naproanilide (RS)-a-2-naphthoxypropionanilide; arylalanine herbicides such as benzoylprop N-benzo
  • quinolinecarboxylic acid herbicides such as quinclorac 3,7-dichloroquinoline-8-carboxylic acid
  • arsenical herbicides such as CMA calcium bis(hydrogen methylarsonate); MAMA ammonium hydrogen methylarsonate; sodium arsenite; benzoylcyclohexanedione herbicides such as mesotrione 2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1 ,3-dione;
  • benzofuranyl alkylsulphonate herbicides such as benfuresate 2,3-dihydro-3,3- dimethylbenzofuran-5-yl ethanesulphonate; carbamate herbicides such as carboxazole methyl 5-ferf-butyl-1 ,2-oxazol-3-ylcarbamate; fenasulam methyl 4-[2-(4-chloro-o- tolyloxy)acetamido]phenylsulphonylcarbamate; carbanilate herbicides such as BCPC ⁇ RS)- sec-butyl 3-chlorocarbanilate; desmedipham ethyl 3-phenylcarbamoyloxyphenylcarbamate; swep methyl 3,4-dichlorocarbanilate; cyclohexene oxime herbicides such as butroxydim (RS)-(EZ)-5-(3-butyryl-2,4,6-trimethylphenyl)-2
  • dithiocarbamate herbicides such as dazomet 3,5-dimethyl-1 ,3,5-thiadiazinane-2-thione; halogenated aliphatic herbicides such as dalapon 2,2-dichloropropionic acid; chloroacetic acid; imidazolinone herbicides such as imazapyr (RS)-2-(4-isopropyl-4-methyl-5-oxo-2- imidazolin-2-yl)nicotinic acid; inorganic herbicides such as disodium tetraborate decahydrate; sodium azide; nitrile herbicides such as chloroxynil 3,5-dichloro-4- hydroxybenzonitrile; ioxynil 4-hydroxy-3,5-di-iodobenzonitrile; organophosphorus herbicides such as anilofos S-4-chloro-N-isopropylcarbaniloylmethyl 0,0-dimethyl phosphorodithioate; glufosinate 4-
  • thiocarbonate herbicides such as EXD 0,0-diethyl dithiobis(thioformate); thiourea herbicides such as methiuron 1 ,1 -dimethyl-3-m-tolyl-2-thiourea; triazine herbicides such as triaziflam (f?S)-/V-[2-(3,5-dimethylphenoxy)-1 -methylethyl]-6-(1 -fluoro-1 -methylethyl)-1 ,3,5- triazine-2,4-diamine; chlorotriazine herbicides such as cyprazine 6-chloro-/V 2 -cyclopropyl-
  • thiadiazolylurea herbicides such as tebuthiuron 1 -(5-feri-butyl-1 ,3,4-thiadiazol-2-yl)-1 ,3- dimethylurea; and/or unclassified herbicides such as chlorfenac (2,3,6- trichlorophenyl)acetic acid; methazole 2-(3,4-dichlorophenyl)-4-methyl-1 ,2,4- oxadiazolidine-3,5-dione; tritac (RS)-1 -(2,3,6-trichlorobenzyloxy)propan-2-ol; 2,4-D, chlorimuron, and fenoxaprop; and combinations thereof.
  • RS tritac
  • Ingredient (h3) is a pesticide. Suitable pesticides are exemplified by atrazine, diazinon, and chlorpyrifos. For purposes of this application, pesticide includes insect repellents such as ⁇ , ⁇ -diethyl-meta-toluamide and pyrethroids such as pyrethrin.
  • Ingredient (h4) is an antimicrobial agent. Suitable antimicrobials are commercially available, such as DOW CORNING® 5700 and DOW CORNING® 5772, which are from Dow Corning Corporation of Midland, Michigan, U.S.A.
  • ingredient (H) may comprise a boron containing material, e.g., boric anhydride, borax, or disodium octaborate tetrahydrate; which may function as a pesticide, fungicide, and/or flame retardant.
  • a boron containing material e.g., boric anhydride, borax, or disodium octaborate tetrahydrate
  • Ingredient (I) is a stabilizer that may be used for altering the reaction rate of the composition, as compared to a composition containing the same ingredients but with the stabilizer omitted.
  • Stabilizers for hydrosilylation curable compositions are exemplified by acetylenic alcohols such as methyl butynol, ethynyl cyclohexanol, dimethyl hexynol, and 3,5-dimethyl-1 -hexyn-3-ol, 1 -butyn-3-ol, 1 -propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1 - butyn-3-ol, 3-methyl-1 -pentyn-3-ol, 3-phenyl-1 -butyn-3-ol, 4-ethyl-1 -octyn-3-ol, 3,5- diemthyl-1 -hexyn-3-ol, and 1 -ethynyl-1
  • cycloalkenylsiloxanes such as methylvinylcyclosiloxanes exemplified by 1 ,3,5,7- tetramethyl-1 ,3,5,7-tetravinylcyclotetrasiloxane, 1 ,3,5,7-tetramethyM ,3,5,7- tetrahexenylcyclotetrasiloxane, and a combination thereof; ene-yne compounds such as 3- methyl-3-penten-1 -yne, 3,5-dimethyl-3-hexen-1 -yne; triazoles such as benzotriazole;
  • phosphines such as tetramethyl ethylenediamine, dialkyi fumarates, dialkenyl fumarates, dialkoxyalkyl fumarates, maleates such as diallyl maleate; nitriles; ethers; carbon monoxide; alkenes such as cyclo-octadiene,
  • divinyltetramethyldisiloxane ethylene glycol dimethacrylate
  • alcohols such as benzyl alcohol
  • a combination thereof benzyl alcohol
  • ingredient (I) in the composition may be a silylated acetylenic compound.
  • silylated acetylenic compound reduces yellowing of the reaction product prepared from
  • hydrosilylation reaction of the composition as compared to a reaction product from hydrosilylation of a composition that does not contain a silylated acetylenic compound or that contains an organic acetylenic alcohol stabilizer, such as those described above.
  • the silylated acetylenic compound is exemplified by (3-methyl-1 -butyn-3- oxy)trimethylsilane, ((1 ,1 -dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1 -butyn-3- oxy)dimethylsilane, bis(3-methyl-1 -butyn-3-oxy)silanemethylvinylsilane, bis((1 ,1 -dimethyl-2- propynyl)oxy)dimethylsilane, methyl(tris(1 ,1 -dimethyl-2-propynyloxy))silane, methyl(tris(3- methyl-1 -butyn-3-oxy))silane, (3-methyl-1 -butyn-3-oxy)dimethylphenylsilane, (3-methyl-1 - butyn-3-oxy)dimethylhexenylsilane, (3-methyl-1 -buty
  • ingredient (I) is exemplified by methyl(tris(1 ,1 -dimethyl-2-propynyloxy))silane, ((1 ,1 - dimethyl-2-propynyl)oxy)trimethylsilane, or a combination thereof.
  • the silylated acetylenic compound useful as ingredient (I) may be prepared by methods known in the art, such as silylating an acetylenic alcohol described above by reacting it with a chlorosilane in the presence of an acid receptor.
  • the amount of stabilizer added to the composition will depend on various factors including the desired pot life of the composition, whether the composition will be a one part composition or a multiple part composition, the particular stabilizer used, and the selection and amount of ingredient (C), if present. However, when present, the amount of stabilizer may range from 0 % to 1 %, alternatively 0% to 5%, alternatively 0.001 % to 1 %, alternatively 0.01 % to 0.5 %, and alternatively 0.0025 % to 0.025 %, based on the weight of all ingredients in the composition.
  • Ingredient (J) is a flame retardant.
  • Suitable flame retardants may include, for example, carbon black, hydrated aluminum hydroxide, and silicates such as wollastonite, platinum and platinum compounds.
  • the flame retardant may be selected from halogen based flame-retardants such as decabromodiphenyloxide, octabromodiphenyl oxide, hexabromocyclododecane, decabromobiphenyl oxide, diphenyoxybenzene, ethylene bis- tetrabromophthalmide, pentabromoethyl benzene, pentabromobenzyl acrylate, tribromophenyl maleic imide, tetrabromobisphenyl A, bis-(tribromophenoxy) ethane, bis- (pentabromophenoxy) ethane, polydibomophenylene oxide, tribromophenylallyl ether, bis- dibro
  • the flame retardant may be selected from phosphorus based flame-retardants such as (2,3- dibromopropyl)-phosphate, phosphorus, cyclic phosphates, triaryl phosphate, bis- melaminium pentate, pentaerythritol bicyclic phosphate, dimethyl methyl phosphate, phosphine oxide diol, triphenyl phosphate, tris- (2-chloroethyl) phosphate, phosphate esters such as tricreyl, trixylenyl, isodecyl diphenyl, ethylhexyl diphenyl, phosphate salts of various amines such as ammonium phosphate, trioctyl, tributyl or tris-butoxyethyl phosphate ester.
  • phosphorus based flame-retardants such as (2,3- dibromopropyl)-phosphate, phosphorus, cycl
  • flame retardants may include tetraalkyl lead compounds such as tetraethyl lead, iron pentacarbonyl, manganese methyl cyclopentadienyl tricarbonyl, melamine and derivatives such as melamine salts, guanidine, dicyandiamide, ammonium sulphamate, alumina trihydrate, and magnesium hydroxide alumina trihydrate.
  • tetraalkyl lead compounds such as tetraethyl lead, iron pentacarbonyl, manganese methyl cyclopentadienyl tricarbonyl, melamine and derivatives such as melamine salts, guanidine, dicyandiamide, ammonium sulphamate, alumina trihydrate, and magnesium hydroxide alumina trihydrate.
  • the amount of flame retardant will vary depending on factors such as the flame retardant selected and whether solvent is present. However, the amount of flame retardant in the composition may range from greater than 0 % to 10 % based on the weight of all ingredients in the composition.
  • Ingredient (K) is a surface modifier.
  • Suitable surface modifiers are exemplified by (k1 ) an adhesion promoter and (k2) a release agent.
  • Suitable adhesion promoters for ingredient (k1 ) may comprise a transition metal chelate, a hydrocarbonoxysilane such as an alkoxysilane, a combination of an alkoxysilane and a hydroxy-functional
  • Adhesion promoters are known in the art and may comprise silanes having the formula
  • R19 R R 20 s Si(OR 21 )4_( r + S ) where each R 1 9 is independently a monovalent organic group having at least 3 carbon atoms;
  • R 20 contains at least one SiC bonded substituent having an adhesion-promoting group, such as amino, epoxy, mercapto or acrylate groups;
  • subscript r has a value ranging from 0 to 2; subscript s is either 1 or 2; and the sum of (r + s) is not greater than 3.
  • the adhesion promoter may comprise a partial condensate of the above silane.
  • the adhesion promoter may comprise a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane.
  • the adhesion promoter may comprise an unsaturated or epoxy- functional compound.
  • the adhesion promoter may comprise an unsaturated or epoxy- functional alkoxysilane.
  • the functional alkoxysilane can have the formula
  • Each R 22 is independently a monovalent organic group with the proviso that at least one R 22 is an unsaturated organic group or an epoxy-functional organic group.
  • Epoxy-functional organic groups for R 22 are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl.
  • Unsaturated organic groups for R 22 are exemplified by 3-methacryloyloxypropyl, 3- acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecylenyl.
  • Each R 23 is independently a saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms.
  • R 23 is exemplified by Me, Et, Pr, and Bu.
  • Examples of suitable epoxy-functional alkoxysilanes include 3- glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,
  • suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3- methacryloyloxypropyl triethoxysilane, 3-acryloyloxypropyl trimethoxysilane, 3- acryloyloxypropyl triethoxysilane, and combinations thereof.
  • the adhesion promoter may comprise an epoxy-functional siloxane such as a reaction product of a hydroxy-terminated polyorganosiloxane with an epoxy- functional alkoxysilane, as described above, or a physical blend of the hydroxy-terminated polyorganosiloxane with the epoxy-functional alkoxysilane.
  • the adhesion promoter may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane.
  • the adhesion promoter is exemplified by a mixture of 3- glycidoxypropyltrimethoxysilane and a reaction product of hydroxy-terminated
  • methylvinylsiloxane with 3-glycidoxypropyltrimethoxysilane or a mixture of 3- glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated
  • the adhesion promoter may comprise an aminofunctional silane, such as an aminofunctional alkoxysilane exemplified by H2N(CH2)2Si(OCH3)3,
  • the adhesion promoter may comprise a transition metal chelate.
  • Suitable transition metal chelates include titanates, zirconates such as zirconium acetylacetonate, aluminum chelates such as aluminum acetylacetonate, and combinations thereof.
  • the adhesion promoter may comprise a combination of a transition metal chelate with an alkoxysilane, such as a combination of
  • Ingredient (k2) is a release agent.
  • Suitable release agents are exemplified by fluorinated compounds, such as fluoro-functional silicones, or fluoro-functional organic compounds.
  • the surface modifier for ingredient (K) may be used to change the appearance of the surface of a reaction product of the composition.
  • surface modifier may be used to increase gloss of the surface of a reaction product of the composition.
  • Such a surface modifier may comprise a polydiorganosiloxane with alkyl and aryl groups.
  • DOW CORNING® 550 Fluid is a trimethylsiloxy-terminated poly(dimethyl/methylphenyl)siloxane with a viscosity of 125 cSt that is commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.
  • ingredient (K) may be a natural oil obtained from a plant or animal source, such as linseed oil, tung oil, soybean oil, castor oil, fish oil, hempseed oil, cottonseed oil, oiticica oil, or rapeseed oil.
  • ingredient (K) depends on various factors including the type of surface modifier selected as ingredient (K) and the end use of the composition and its reaction product. However, ingredient (K), when present, may be added to the composition in an amount ranging from 0.01 to 50 weight parts based on the weight of the composition, alternatively 0.01 to 10 weight parts, and alternatively 0.01 to 5 weight parts. Ingredient (K) may be one adhesion promoter. Alternatively, ingredient (K) may comprise two or more different surface modifiers that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence.
  • Chain lengtheners may include difunctional silanes and difunctional siloxanes, which extend the length of polyorganosiloxane chains before crosslinking occurs. Chain lengtheners may be used to reduce the modulus of elongation of the cured product. Chain lengtheners compete in their reactions with aliphatically unsaturated groups and/or silicon bonded hydrogen atoms in other ingredients of the composition, e.g., ingredients (B) and/or ingredient (C), when present. Dimethylhydrogensiloxy-terminated polydimethylsiloxanes having relatively low degrees of polymerization ⁇ e.g., DP ranging from 3 to 50) may be used as ingredient (L).
  • DP ranging from 3 to 50
  • Ingredient (L) may be one chain lengthener Alternatively, ingredient (L) may comprise two or more different chain lengtheners that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence [0207]
  • Ingredient (M) is and endblocker comprising an M-unit, i.e., a siloxane unit of formula R 24 3SiO-
  • Ingredient (M) may comprise polyorganosiloxanes endblocked on one terminal end by a triorganosilyl group, e.g., (CH3)3SiO-, and on the other end by a silicon bonded hydrogen atom and/or an aliphatically unsaturated organic group.
  • Ingredient (M) may be a polydiorganosiloxane such as a polydimethylsiloxane.
  • polydiorganosiloxanes having both silicon bonded hydrogen terminals and triorganosilyl end groups may have more than 50 %, alternatively more than 75 %, of the total end groups as silicon bonded hydrogen atoms.
  • the amount of triorganosilyl group in the polydimethylsiloxane may be used to regulate the modulus of a cured product prepared by curing the composition. Without wishing to be bound by theory, it is thought that higher concentrations of triorganosilyl end groups may provide a lower modulus in cured products.
  • Ingredient (M) may be one endblocker. Alternatively, ingredient (M) may comprise two or more different endblockers that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence.
  • Ingredient (N) is a flux agent.
  • the composition may comprise 0 % to 2 % of the flux agent based on the weight of all ingredients in the composition.
  • Molecules containing chemically active functional groups such as carboxylic acid and amines can be used as flux agents.
  • Such flux agents can include aliphatic acids such as succinic acid, abietic acid, oleic acid, and adipic acid; aromatic acids such as benzoic acids; aliphatic amines and their derivatives, such as triethanolamine, hydrochloride salts of amines, and hydrobromide salts of amines. Flux agents are known in the art and are commercially available.
  • Ingredient (O) is an anti-aging additive.
  • the anti-aging additive may comprise an antioxidant, a UV absorber, a UV stabilizer, a heat stabilizer, or a combination thereof.
  • Suitable antioxidants are known in the art and are commercially available. Suitable antioxidants include phenolic antioxidants and combinations of phenolic antioxidants with stabilizers. Phenolic antioxidants include fully sterically hindered phenols and partially hindered phenols; and sterically hindered amines such as tetramethyl-piperidine derivatives. Suitable phenolic antioxidants include vitamin E and IRGANOX® 1010 from Ciba Specialty Chemicals, U.S.A.
  • IRGANOX® 1010 comprises pentaerythritol tetrakis(3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate).
  • UV absorbers include phenol, 2- (2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-, branched and linear (TINUVIN® 571 ).
  • UV stabilizers examples include bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) sebacate; methyl 1 ,2,2,6,6-pentamethyl-4-piperidyl/sebacate; and a combination thereof (TINUVIN® 272).
  • TINUVIN® 272 examples include bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) sebacate; methyl 1 ,2,2,6,6-pentamethyl-4-piperidyl/sebacate; and a combination thereof (TINUVIN® 272).
  • TINUVIN® 765 are commercially available from Ciba Specialty Chemicals of Tarrytown, NY, U.S.A.
  • Other UV and light stabilizers are commercially available, and are exemplified by LowLite from Chemtura, OnCap from PolyOne, and Light Stabilizer 210 from E. I. du Pont de Nemours and Company of Delaware, U.S.A.
  • Oligomeric (higher molecular weight) stabilizers may alternatively be used, for example, to minimize potential for migration of the stabilizer out of the composition or the cured product thereof.
  • An example of an oligomeric antioxidant stabilizer specifically, hindered amine light stabilizer (HALS)
  • HALS hindered amine light stabilizer
  • Ciba TINUVIN® 622 which is a dimethylester of butanedioic acid copolymerized with 4-hydroxy-2,2,6,6- tetramethyl-1 -piperidine ethanol.
  • Heat stabilizers may include iron oxides and carbon blacks, iron carboxylate salts, cerium hydrate, barium zirconate, cerium and zirconium octoates, and porphyrins.
  • the amount of ingredient (O) depends on various factors including the specific anti-aging additive selected and the anti-aging benefit desired. However, the amount of ingredient (O) may range from 0 to 5 weight %, alternatively 0.1 % to 4 %, and alternatively 0.5 to 3 weight %, based on the weight of all ingredients in the composition. Ingredient (O) may be one anti-aging additive. Alternatively, ingredient (O) may comprise two or more different anti-aging additives.
  • Ingredient (P) is a pigment.
  • the term 'pigment' includes any ingredient used to impart color to a reaction product of a composition described herein.
  • the amount of pigment depends on various factors including the type of pigment selected and the desired degree of coloration of the product.
  • the composition may comprise 0 to 20 %, alternatively 0.001 % to 5 %, of a pigment based on the weight of all ingredients in the composition.
  • suitable pigments include indigo, titanium dioxide Stan-Tone 50SP01 Green (which is commercially available from PolyOne) and carbon black.
  • carbon black include Shawinigan Acetylene black, which is commercially available from Chevron Phillips Chemical Company LP; SUPERJET® Carbon Black (LB-101 1 ) supplied by Elementis Pigments Inc., of Fairview Heights, IL U.S.A.; SR 51 1 supplied by Sid Richardson Carbon Co, of Akron, OH U.S.A.; and N330, N550, N762, N990 (from Degussa Engineered Carbons of Parsippany, NJ, U.S.A.).
  • Ingredient (Q) is an acid acceptor. Suitable acid acceptors include magnesium oxide, calcium oxide, and combinations thereof.
  • the composition may comprise 0 % to 2 % of ingredient (Q) based on the weight of the composition.
  • the composition may optionally further comprise up to 5 %, alternatively 1 % to 2 % based on the weight of the composition of ingredient (R) a rheological additive for modifying rheology of the composition.
  • Rheological additives are known in the art and are commercially available. Examples include polyamides, Polyvest, which is commercially available from Evonk, Disparlon from King Industries, Kevlar Fibre Pulp from Du Pont, Rheospan from Nanocor, and Ircogel from Lubrizol.
  • Other suitable rheological additives include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate and barium stearate, and combinations thereof.
  • ingredient (R) may comprise a microcrystalline wax that is a solid at 25 °C (wax).
  • the melting point may be selected such that the wax has a melting point at the low end of the desired application temperature range.
  • ingredient (R) acts as a process aid that improves flow properties of the composition.
  • incorporation of wax may also facilitate incorporation of fillers, compounding and de-airing (during production of the composition), and mixing (static or dynamic mixing during application of parts of a multiple part composition).
  • the wax when molten, serves as a process aid, substantially easing the incorporation of filler in the composition during compounding, the compounding process itself, as well as in during a de-airing step, if used.
  • the wax with a melt temperature below 100 °C, may facilitate mixing of the parts of a multiple part composition before application, even in a simple static mixer.
  • Waxes suitable for use as ingredient (R) may be non-polar hydrocarbons.
  • the waxes may have branched structures, cyclic structures, or combinations thereof.
  • petroleum microcrystalline waxes are available from Strahl & Pitsch, Inc., of West Arabic, NY, U.S.A.
  • SP 96 melting point ranging from 62 2 C to 69 2 C
  • SP 18 melting point ranging from 73 2 C to 80 2 C
  • SP 19 melting point ranging from 76 2 C to 83 2 C
  • SP 26 melting point ranging from 76 2 C to 83 2 C
  • SP 60 melting point ranging from 79 2 C to 85 2 C
  • SP 617 melting point ranging from 88 2 C to 93 2 C
  • SP 89 melting point ranging from 90 2 C to 95 2 C
  • SP 624 melting point ranging from 90 2 C to 95 2 C
  • Multiwax® W-445 which comprises saturated branched and cyclic non-polar hydrocarbons, and has melting point ranging from 73 2 C to 80 2 C.
  • the amount of ingredient (R) depends on various factors including the specific rheological additive selected and the selections of the other ingredients of the composition. However, the amount of ingredient (R) may range from 0 parts to 20 parts, alternatively 1 parts to 15 parts, and alternatively 1 part to 5 parts based on the weight of all ingredients in the composition. Ingredient (R) may be one rheological additive. Alternatively, ingredient (R) may comprise two or more different rheological additives.
  • a vehicle may be used in the composition.
  • the vehicle may facilitate flow of the composition and introduction of certain ingredients, such as silicone resin.
  • Vehciles used herein are those that help fluidize the ingredients of the composition but essentially do not react with the ingredients.
  • the vehicle may be selected based on solubility the ingredients in the composition and volatility.
  • the solubility refers to the vehicle being sufficient to dissolve and/or disperse ingredients of the composition.
  • Volatility refers to vapor pressure of the vehicle. If the vehicle is too volatile (having too high vapor pressure) bubbles may form in the composition during hydrosilylation reaction, and the bubbles may cause cracks or otherwise weaken or detrimentally affect properties of the reaction product. However, if the vehicle is not volatile enough (too low vapor pressure) the vehicle may remain as a plasticizer in the reaction product of the composition.
  • Suitable vehicles include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane and other low molecular weight polyorganosiloxanes, such as 0.5 to 1 .5 cSt Dow Corning® 200 Fluids and Dow Corning® OS FLUIDS, which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.
  • suitable vapor pressures such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane and other low molecular weight polyorganosiloxanes, such as 0.5 to 1 .5 cSt Dow Corning® 200 Fluids and Dow Corning® OS FLUIDS, which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.
  • the vehicle may comprise an organic solvent.
  • the organic solvent can be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n- butyl ether, a halogenated hydrocarbon such as dichloromethane, 1 ,1 ,1 -trichloroethane or methylene chloride; chloroform; dimethyl s
  • the amount of vehicle will depend on various factors including the type of vehicle selected and the amount and type of other ingredients selected for the composition.
  • the amount of vehicle may range from 1 % to 99%, alternatively 2 % to 50 %, based on the weight of all ingredients in the composition.
  • Ingredient (S) can be added during preparation of the composition, for example, to aid mixing and delivery. All or a portion of ingredient (S) may optionally be removed after the composition is prepared.
  • Ingredient (T) is a surfactant. Suitable surfactants include silicone polyethers, ethylene oxide polymers, propylene oxide polymers, copolymers of ethylene oxide and propylene oxide, other non-ionic surfactants, and combinations thereof.
  • the composition may comprise 0 % to 0.05 % of the surfactant based on the weight of all ingredients in the composition.
  • Ingredient (U) is a corrosion inhibitor.
  • suitable corrosion inhibitors include benzotriazole, mercaptabenzotriazole and commercially available corrosion inhibitors such as 2,5-dimercapto-1 ,3,4-thiadiazole derivative (CUVAN® 826) and alkylthiadiazole (CUVAN® 484) from R. T. Vanderbilt of Norwalk, Connecticut, U.S.A.
  • the amount of ingredient (U) may range from 0.05 % to 0.5 % based on the weight of the composition.
  • ingredients for the composition described above there may be overlap between types of ingredients because certain ingredients described herein may have more than one function.
  • certain alkoxysilanes may be useful as filler treating agents and as adhesion promoters
  • certain plasticizers such as fatty acid esters may also be useful as filler treating agents.
  • Certain particulates may be useful as fillers and as pigments, and even as flame retardants, e.g., carbon black.
  • the additional ingredients are distinct from one another.
  • composition can be prepared by a method comprising combining all ingredients by any convenient means such as mixing at ambient or elevated temperature.
  • Ingredient (I) when present, may be added before ingredient (A), for example, when the composition will be prepared at elevated temperature and/or the composition will be prepared as a one part composition.
  • the composition may optionally be prepared by surface treating a particulate ingredient ⁇ e.g., filler and/or spacer, if present) with ingredient (G), and thereafter mixing the product thereof with the other ingredients of the composition.
  • a particulate ingredient e.g., filler and/or spacer, if present
  • the composition may be prepared as a multiple part composition, for example, when ingredient (I) is absent, or when the composition will be stored for a long period of time before use.
  • ingredient (A) is stored in a separate part from any ingredient having a silicon bonded hydrogen atom, for example ingredient (C), and the parts are combined shortly before use of the composition.
  • a two part composition may be prepared by combining ingredients comprising (B), (A), (F), and optionally one or more other additional ingredients described above to form a base by any convenient means such as mixing.
  • a curing agent may be prepared by combining ingredients comprising (B), (C), and optionally one or more other additional ingredients described above by any convenient means such as mixing.
  • the ingredients may be combined at ambient or elevated temperature.
  • the weight ratio of amounts of base to curing agent may range from 1 :1 to 10:1 .
  • the composition will react via hydrosilylation reaction to form a reaction product.
  • the reaction product may have various forms, such as a silane, a gum, a gel, a rubber, or a resin.
  • the aliphatically unsaturated compound can be styrene (B1 ), 1 -octene (B2), or 1 - hexene (B3), all of which are also available from Sigma-Aldrich.
  • the aliphatically unsaturated compound can be (B4) a vinyl terminated polydimethylsiloxane, containing 2.6 meq silicon bonded vinyl groups and having Mw of 9400 and viscosity of 200 cSt, which is commercially available as DMS-V22 from Gelest, Inc. of Morrisville, Pennsylvania, U.S.A.
  • the SiH functional compound can be (C1 ) a trimethylsiloxy-terminated,
  • the SiH functional compound can be (C2) Phenylsilane (' ⁇ ⁇ '), which is commercially available from Sigma-Aldrich.
  • the control catalyst was DOW CORNING® 2-0707 INT, which is a complex of Pt with a polyorganosiloxane.
  • DOW CORNING® 2-0707 INT is commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.
  • One or more of the following model reactions may be used to test catalytic activity of a reaction product prepared as described above for ingredient (A).
  • Ingredients (B3) and (C2) were used in the [PhSi] reaction to attempt to make a reaction product [I] comprising PhSiH z (C6H-
  • Ingredients (B3) and (C1 ) were used in the [HMTS] reaction to attempt to make a reaction product [II] comprising (H3C)3Si-0-Si(CH2)(C6H-
  • N1I2 purchased from Strem Chemicals, 0.273 gm (0.87 mmol), was dissolved in 14.8 gm THF and was cooled at -35 °C.
  • Lithium bis(trimethylsilyl)amide (1 M in THF) purchased from Aldrich, 1 .64 gm (1 .84 mmol), was mixed with 14.8 gm THF and added slowly into the N1I2 solution at -35 °C under agitation. The solution turned from green/brown to dark brown after the addition of Lithium bis(trimethylsilyl)amide solution. The temperature was raised to room temperature and heated to 60 °C for 3 hours under agitation. The resulting solution at 0.025 M was used as precursor Ni-2 in the examples below.
  • Precursor solutions were prepared by mixing a Ni precursor at a 0.025 molar (M) concentration with THF or, if the precursor was insoluble in THF, then a suitable solvent to dissolve the ligand selected from dimethylsulfoxide (DMSO), toluene, and hexane. Nickel (II) bromide dimethoxyethane, and Nickel (II) bis trimethylsilyl amide were used as the Ni precursors. Solutions of each ligand shown above in Table 2 were also prepared by mixing the ligand at a 0.025 M concentration with THF. Each ligand solution prepared above was dispensed into 2 milliliter (mL) vials at 85 microliters ( ⁇ ) per vial.
  • M dimethylsulfoxide
  • ⁇ microliters
  • one of the metal precursor solutions described above was added to a vial containing a ligand, and an additional 85 microliters ( ⁇ ) THF was added, and the vial contents were mixed at 300 RPM at room temperature of 25 °C for 2 hours.
  • a sufficient amount of metal precursor solution was added such that the Metal : Ligand Ratio was either 1 : 1 or 1 : 2.
  • the resulting mixture in the vial was cooled to a temperature of - 17 °C.
  • An activator was added, and the vial was allowed to return to room temperature. The activator was 95 ⁇ L ⁇ at 0.05 M concentration of either LiBArF in THF or NaEt3BH in toluene.
  • the vial contents were mixed for 2 hours.
  • the resulting vial contents were evaluated for use in catalyzing hydrosilylation.
  • Example 2 [PhSi] Reaction
  • PhSiH3 (C2) in dodecane and 1 -hexene (B3) were added to a vial prepared according to Example 1 .
  • the amount of PhSiH3 (C2) added to the vial was either 170 ⁇ _ of 6.25 M (as H or SiH) PhSiH3 (C2) in dodecane, or 132.4 ⁇ _
  • PhSiH3 (C2) in 37.6 ⁇ L ⁇ dodecane The amount of 1 -hexene (B3) was 145 ⁇ _.
  • Each vial was mixed overnight (for 16 h) at 50 °C. The resulting contents of each vial were analyzed by GC according to the method described below.
  • a gas chromatography (GC) analysis was made of the samples prepared in an example above.
  • the GC analysis was performed with a Hewlett-Packard 7890A gas chromatograph with a flame ionization detector (FID).
  • FID flame ionization detector
  • a Leap Combi-Pal robot was used to perform the injections in an automated manner.
  • the system was configured as detailed in Table 3.
  • Dodecane was used as an internal standard to gravimetrically quantify the chromatographic analyses. Internal standard was introduced prior to reaction at 5% (w/w) from a solution of dodecane and phenylsilane. Theoretical response factors for the analytes were calculated and entered into the ChemStation to automatically create a calibration table and quantitatively calculate the concentration of an analyte in the presence of an internal standard (Equation 1 ).
  • Equation 1 The terms in Equation 1 are defined as follows: RF ana
  • s response factor for the internal standard.

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Abstract

A composition contains (A) a hydrosi!ylation reaction catalyst and (B) an aliphatically unsaturated compound having an average, per moiecuie, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosiiyiaiion reaction. The composition is capable of reacting via hydrosiiyiation reaction to form a reaction product, such as a si!ane, a gum, a gel, a rubber, or a resin. Ingredient (A) contains a metai-iigand complex that can be prepared by a method including reacting a metal precursor and a !igand,

Description

NICKEL CONTAINING HYDROSILYLATION CATALYSTS AND COMPOSITIONS
CONTAINING THE CATALYSTS
[0001] Catalysts for catalyzing hydrosilylation reaction are known in the art and are commercially available. Such conventional hydrosilylation catalysts can be a metal selected from platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the hydrosilylation catalyst may be a compound of such a metal, for example, chloroplatinic acid, chloroplatinic acid hexahydrate, platinum dichloride, and complexes of said compounds with low molecular weight organopolysiloxanes or platinum compounds microencapsulated in a matrix or core/shell type structure. Complexes of platinum with low molecular weight organopolysiloxanes include 1 ,3-diethenyl-1 ,1 ,3,3 -tetramethyldisiloxane complexes with platinum. These complexes may be microencapsulated in a resin matrix. Exemplary hydrosilylation catalysts are described in U.S. Patents 3,159,601 ; 3,220,972; 3,296,291 ; 3,419,593; 3,516,946; 3,814,730; 3,989,668; 4,784,879; 5,036,1 17; and 5,175,325 and EP 0 347 895 B. Microencapsulated hydrosilylation catalysts and methods of preparing them are known in the art, as exemplified in U.S. Patents 4,766,176 and 5,017,654.
[0002] These hydrosilylation catalysts suffer from the drawback of being extremely costly. Some of the metals in these hydrosilylation catalysts may also be difficult to obtain, and some of these hydrosilylation catalysts may be difficult to prepare. There is a need in industry to replace the conventional hydrosilylation catalysts described above with a less expensive and/or more readily available alternative.
BRIEF SUMMARY OF THE INVENTION
[0003] A reaction product of ingredients comprising a Nickel precursor (Ni precursor) and a ligand, and methods for preparation of the reaction product are disclosed. A
composition, which is capable of forming a reaction product via hydrosilylation reaction, comprises the reaction product and an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction. When the aliphatically unsaturated compound lacks a silicon bonded hydrogen atom, then the composition further comprises an SiH functional compound having an average, per molecule, of one or more silicon bonded hydrogen atoms.
DETAILED DESCRIPTION OF THE INVENTION
[0004] All amounts, ratios, and percentages are by weight unless otherwise indicated. The articles 'a', 'an', and 'the' each refer to one or more, unless otherwise indicated by the context of specification. The disclosure of ranges includes the range itself and also anything subsumed therein, as well as endpoints. For example, disclosure of a range of 2.0 to 4.0 includes not only the range of 2.0 to 4.0, but also 2.1 , 2.3, 3.4, 3.5, and 4.0 individually, as well as any other number subsumed in the range. Furthermore, disclosure of a range of, for example, 2.0 to 4.0 includes the subsets of, for example, 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7, and 3.8 to 4.0, as well as any other subset subsumed in the range.
Similarly, the disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein. For example, disclosure of the Markush group a hydrogen atom , an alkyi group, an aryl group, or an aralkyl group includes the member alkyi individually; the subgroup alkyi and aryl; and any other individual member and subgroup subsumed therein.
[0005] "Alkyi" means an acyclic, branched or unbranched, saturated monovalent hydrocarbon group. Alkyi is exemplified by, but not limited to, methyl, ethyl, propyl (e.g., iso-propyl and/or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and/or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and/or tert-pentyl), hexyl, heptyl, octyl, nonyl, and decyl, as well as branched saturated monovalent hydrocarbon groups of 6 or more carbon atoms.
[0006] "Aryl" means a cyclic, fully unsaturated, hydrocarbon group. Aryl is exemplified by, but not limited to, cyclopentadienyl, phenyl, anthracenyl, and naphthyl. Monocyclic aryl groups may have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms. Polycyclic aryl groups may have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, and alternatively 12 to 14 carbon atoms.
[0007] "Aralkyl" means an alkyi group having a pendant and/or terminal aryl group or an aryl group having a pendant alkyi group. Exemplary aralkyl groups include tolyl, xylyl, benzyl, phenylethyl, phenyl propyl, and phenyl butyl.
[0008] "Carbocycle" and "carbocyclic" each mean a hydrocarbon ring. Carbocycles may be monocyclic or alternatively may be fused, bridged, or spiro polycyclic rings. Monocyclic carbocycles may have 3 to 9 carbon atoms, alternatively 4 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms. Polycyclic carbocycles may have 7 to 1 7 carbon atoms, alternatively 7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms. Carbocycles may be saturated or partially unsaturated.
[0009] "Cycloalkyl" means saturated carbocycle. Monocyclic cycloalkyl groups are exemplified by cyclobutyl, cyclopentyl, and cyclohexyl.
[0010] "Halogenated hydrocarbon" means a hydrocarbon where one or more hydrogen atoms bonded to a carbon atom have been formally replaced with a halogen atom.
Halogenated hydrocarbon groups include haloalkyl groups, halogenated carbocyclic groups, and haloalkenyl groups. Haloalkyl groups include fluorinated alkyi groups such as trifluoromethyl (CF3), fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4- trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3- nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl; and chlorinated alkyl groups such as chloromethyl and 3-chloropropyl. Halogenated carbocyclic groups include fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4- difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl; and chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl. Haloalkenyl groups include allyl chloride.
[0011] "Heteroatom" means any of the Group 13-17 elements of the lUPAC Periodic Table of the Elements at
http://www.iupac.org/fileadmin/user_upload/news/IUPAC_Periodic_Table-1 Jun12.pdf, except carbon. "Heteroatom" include, for example, N, O, P, S, Br, CI, F, and I.
[0012] "Heteroatom containing group" means an organic group comprised of a carbon atom and that also includes at least one heteroatom. Heteroatom containing groups may include, for example, one or more of acyl, amide, amine, carboxyl, cyano, epoxy, hydrocarbonoxy, imino, ketone, ketoxime, mercapto, oxime, and/or thiol. For example, when the heteroatom containing group contains one or more halogen atoms, then the heteroatom containing group may be a halogenated hydrocarbon group as defined above. Alternatively, when the heteroatom is oxygen, then the heteroatom containing group may be a hydrocarbonoxy group such as an alkoxy group or an alkylalkoxy group.
[0013] "Inorganic heteroatom containing group" means group comprised of at least 1 heteroatom and at least 1 of hydrogen or a different heteroatoms. Heteroatom containing groups may include, for example, one or more of amine, hydroxyl, imino, nitro, oxo, sulfonyl, and/or thiol.
[0014] "Heteroalkyl" group means an acyclic, branched or unbranched, saturated monovalent hydrocarbon group that also includes at least one heteroatom. "Heteroalkyl" includes haloalkyl groups and alkyl groups in which at least one carbon atom has been replaced with a heteroatom such as N, O, P, or S, e.g., when the heteroatom is O, the heteroalkyl group may be an alkoxy group.
[0015] "Heterocycle" and "heterocyclic" each mean a ring group comprised of carbon atoms and one or more heteroatoms in the ring. The heteroatom in the heterocycle may be N, O, P, S, or a combination thereof. Heterocycles may be monocyclic or alternatively may be fused, bridged, or spiro polycyclic rings. Monocyclic heterocycles may have 3 to 9 member atoms in the ring, alternatively 4 to 7 member atoms, and alternatively 5 to 6 member atoms. Polycyclic heterocycles may have 7 to 17 member atoms, alternatively 7 to 14 member atoms, and alternatively 9 to 10 member atoms. Heterocycles may be saturated or partially unsaturated. [0016] "Heteroaromatic" means a fully unsaturated ring containing group comprised of carbon atoms and one or more heteroatoms in the ring. Monocyclic heteroaromatic groups may have 5 to 9 member atoms, alternatively 6 to 7 member atoms, and alternatively 5 to 6 member atoms. Polycyclic heteroaromatic groups may have 10 to 17 member atoms, alternatively 10 to 14 member atoms, and alternatively 12 to 14 member atoms.
Heteroaromatic includes heteroaryl groups such as pyridyl. Heteroaromatic includes heteroaralkyl, i.e., an alkyl group having a pendant and/or terminal heteroaryl group or a heteroaryl group having a pendant alkyl group. Exemplary heteroaralkyl groups include methylpyridyl and dimethylpyridyl.
[0017] Abbreviations used herein are defined as follows. The abbreviation "cP" means centiPoise, and "cSt" means centiStokes. "DP" means the degree of polymerization.
"FTIR" means Fourier transform infrared spectroscopy. "GC" means gas chromatography. "GPC" means gel permeation chromatography. "Mn" means number average molecular weight. Mn may be measured using GPC. "Mw" means weight average molecular weight. "NMR" means nuclear magnetic resonance. "Pa s" means Pascal seconds, and "ppm" means parts per million. "COD" means cyclooctadienyl. "Et" means ethyl. "Me" means methyl. "Ph" means phenyl. "Pr" means propyl and includes various structures such as iPr and nPr. "iPr" means isopropyl. "nPr" means normal propyl. "Bu" means butyl and includes various structures including nBu, sec-butyl, tBu, and iBu. "iBu" means isobutyl. "nBu" means normal butyl. "tBu" means tert-butyl. "AcAc" means acetyl acetonate. "2- EHA" means 2-ethylhexanoate. "OAc" means acetate. "Hex" means hexenyl. "THF" means tetrahydrofuran. "Vi" means vinyl.
[0018] "M-unit" means a siloxane unit having formula R3S1O-1 /2, where each R independently represents a monovalent atom or organic group. "D-unit" means a siloxane unit having formula R2Si02/2> where each R independently represents a monovalent atom or group. "T-unit" means a siloxane unit having formula RS1O3/2, where each R independently represents a monovalent atom or group. "Q-unit" means a siloxane unit having formula S1O4/2.
[0019] "Non-functional" means that the ingredient does not have either an aliphatically unsaturated substituent or a silicon bonded hydrogen atom that participates in a hydrosilylation reaction.
[0020] "Free of" means that the composition contains a non-detectable amount of the ingredient, or the composition contains an amount of the ingredient insufficient to change the GC measurement measured as described in the Examples section, as compared to the same composition with the ingredient omitted. For example, the composition described herein may be free of platinum catalysts. "Free of platinum catalysts" means that the composition contains a non-detectable amount of a platinum catalyst capable of catalyzing a hydrosilylation reaction with the unsaturated groups on other ingredients in the composition, or the composition contains an amount of a platinum catalyst insufficient to change the GC measurement measured as described in the Examples section, as compared to the same composition with the platinum catalyst omitted. The composition may be free of conventional metal catalysts. "Free of conventional metal catalysts" means that the composition contains a non-detectable amount of a the metal selected from Pt, Rh, Ru, Pd, Os, and Ir, or the compound of such a metal capable of catalyzing a hydrosilylation reaction with the unsaturated groups on other ingredients in the composition, or the composition contains an amount of the conventional metal catalyst insufficient to change the GC measurement measured as described in the Examples section, as compared to the same composition with the conventional metal catalyst omitted. Alternatively, the composition described herein may be free of hydrosilylation reaction catalysts (i.e., free of any ingredient capable of catalyzing a hydrosilylation reaction of the aliphatically unsaturated groups on ingredient (B), described below, other than ingredient (A) described herein).
[0021] The composition, which has at least one ingredient capable of reacting by hydrosilylation reaction (composition), comprises:
(A) a Ni containing hydrosilylation reaction catalyst, and
(B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction.
[0022] Without wishing to be bound by theory, it is thought that the Nicontaining hydrosilylation reaction catalyst is characterizable as being effective for catalyzing the hydrosilylation reaction of the composition. The hydrosilylation reaction of the composition prepares a reaction product. The reaction product may have a form selected from the group consisting of a silane, a gum, a gel, a rubber, and a resin.
[0023] When ingredient (B) does not contain a silicon bonded hydrogen atom, then the composition further comprises ingredient (C), an SiH functional compound having an average, per molecule, of one or more silicon bonded hydrogen atoms, which is distinct from ingredients (A) and (B).
[0024] The composition may optionally further comprise one or more additional ingredients, which are distinct from ingredient (A), ingredient (B), and ingredient (C) described above. Suitable additional ingredients are exemplified by (D) a spacer; (E) an extender, a plasticizer, or a combination thereof; (F) a filler; (G) a filler treating agent; (H) a biocide; (I) a stabilizer, (J) a flame retardant; (K) a surface modifier; (L) a chain lengthener; (M) an endblocker; (N) a flux agent; (O) an anti-aging additive; (P) a pigment; (Q) an acid acceptor (R) a rheological additive; (S) a vehicle; (T) a surfactant; (U) a corrosion inhibitor; and a combination thereof.
[0025] Ingredient (A) is a Ni containing hydrosilylation reaction catalyst. The Ni containing hydrosilylation reaction catalyst comprises, or is prepared with, the reaction product of the Ni precursor and the ligand. Without wishing to be bound by theory, it is thought that this reaction product comprises a Ni-ligand complex. The Ni precursor is distinct from the Ni-ligand complex. The Ni precursor is distinct from the reaction product of the Ni precursor and the ligand.
[0026] The Ni precursor may be a metal compound having general formula (i): N1-A2, where each A is independently a displaceable substituent. Without wishing to be bound by theory, it is thought that one or more instances of A can be displaced from Ni by the ligand to form the Ni-ligand complex. Without wishing to be bound by theory, it is thought that one or more instances of group A are displaced by a complexation reaction between the Ni precursor and the ligand to form the Ni-ligand complex. Each instance of A in general formula (i) may be the same or different. Examples for A include halogen atoms and monovalent organic groups. The monovalent organic group may be a monovalent hydrocarbon group or a monovalent heteroatom containing group. The monovalent heteroatom containing group is exemplified by amino groups, halogenated hydrocarbon groups, silazane groups, carboxylate groups, carboxylic ester groups, carbonyl groups, hydrocarbonoxy groups, sulfonate ester groups, sulfonylimide groups, acetate groups, and cyano groups.
[0027] Examples of halogen atoms for A in general formula (i) include Br, CI, or I.
Examples of monovalent halogenated hydrocarbon groups for A include haloalkyl groups, e.g., fluorinated alkyl groups such as CF3, fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3,3,3- trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3- heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl; and chlorinated alkyl groups such as chloromethyl and 3-chloropropyl; halogenated carbocyclic groups such as fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3- difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl; and chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl; and haloalkenyl groups such as allyl chloride.
[0028] Examples of monovalent hydrocarbon groups for A in general formula (i) include, but are not limited to, alkyl, alkenyl, carbocyclic, aryl, and aralkyl. Alkyl groups are exemplified by Me, Et, Pr, Bu, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, dodecyl, undecyl, and octadecyl. Alkenyl groups are exemplified by Vi, allyl, propenyl, and Hex. Carbocyclic groups are exemplified by saturated carbocyclic groups, e.g., cycloalkyl such as cyclopentyl and cyclohexyl, or unsaturated carbocyclic groups, e.g., cycloalkenyl such as cyclopentadienyl, cyclohexenyl, or cyclooctadienyl. Aryl groups are exemplified by Ph, tolyl, xylyl, mesityl, and naphthyl. Aralkyl groups are exemplified by benzyl and 2- phenylethyl.
[0029] Examples of amino groups for A in general formula (i) have formula -NA'2, where each A' is independently a hydrogen atom or a monovalent hydrocarbon group. Exemplary monovalent hydrocarbon groups for A' include, but are not limited to, alkyl such as Me, Et, Pr, Bu, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, dodecyl, undecyl, and octadecyl; alkenyl such as vinyl, allyl, propenyl, and Hex; carbocyclic groups exemplified by saturated carbocyclic groups, e.g., cycloalkyl such as cyclopentyl and cyclohexyl, or unsaturated carbocyclic groups such as cyclopentadienyl or cyclooctadienyl; aryl such as Ph, tolyl, xylyl, mesityl, and naphthyl; and aralkyl such as benzyl or 2-phenylethyl. Alternatively, each A' may be a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, such as Me or Et.
[0030] Alternatively, each A in general formula (i) may be a silazane group.
[0031] Alternatively, each A in general formula (i) may be a carboxylic ester group. Examples of suitable carboxylic ester groups for A include, but are not limited to OAc, ethylhexanoate (such as 2-EHA), neodecanoate, octanoate, and stearate.
[0032] Examples of monovalent hydrocarbonoxy groups for A in general formula (i) may have formula -O-A", where A" is a monovalent hydrocarbon group. Examples of monovalent hydrocarbon groups for A" include, but are not limited to, alkyl such as Me, Et, Pr, Bu, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, dodecyl, undecyl, and octadecyl; alkenyl such as Vi, allyl, propenyl, and Hex; cycloalkyl such as cyclopentyl and cyclohexyl; aryl such as Ph, tolyl, xylyl, and naphthyl; aralkyl such as benzyl or 2-phenylethyl.
Alternatively, each A" may be an alkyl group, such as Me, Et, nPr, iPr, nBu, iBu, or tBu.
Alternatively, each A" may be an alkyl group, and alternatively each A" may be Et, Pr such as iPr or nPr, or Bu.
[0033] Alternatively, each A in general formula (i) may be an alkyl group, such as Me, Et, nPr, iPr, nBu, iBu, or tBu. Alternatively, each A may be independently selected from the group consisting of Et, benzyl, mesityl, Ph, NEt2, NMe2, cyclooctadiene, ethoxide, iPr, Bu,
2-EHA, ethoxy, propoxy, methoxy, and carbonyl. [0034] Alternatively, the Ni precursor may be a commercially available compound, such as those shown below in Table 1 .
Table 1 - Ni Precursors
Figure imgf000009_0001
[0035] In Table 1 , "Strem" refers to Strem Chemicals Inc. of Newburyport,
Massachusetts, U.S.A.
[0036] The ligand is an organic compound that coordinates with Ni. In the general formulae herein, the monovalent organic groups may be monovalent hydrocarbon groups or monovalent heteroatom containing groups. Examples of monovalent hydrocarbon groups include, but are not limited to, alkyl such as Me, Et, Pr, Bu, pentyl, or hexyl; alkenyl such as vinyl, allyl, propenyl, and hexenyl; carbocyclic groups exemplified by saturated carbocyclic groups, e.g., cycloalkyl such as cyclopentyl and cyclohexyl, or unsaturated carbocyclic groups such as cyclopentadienyl or cyclooctadienyl; aryl such as Ph and naphthyl; aralkyi such as benzyl, tolyl, xylyl, mesityl, or 2-phenylethyl.
[0037] Examples of monovalent heteroatom containing groups in the general formulae include a halogenated hydrocarbon group or a hydrocarbonoxy group. Examples of monovalent halogenated hydrocarbon groups include haloalkyi groups such as fluorinated alkyl groups, e.g., CF3, fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, and
4,4,4-trifluorobutyl; and chlorinated alkyl groups such as chloromethyl. Examples of hydrocarbonoxy groups include alkoxy and aralkyloxy. Alkoxy groups are exemplified by OMe, OEt, OPr, and OBu; alternatively OMe. Aralkyloxy groups are exemplified by phenylmethoxy and phenylethoxy. Alternatively, the monovalent heteroatom containing group may be an aryl group or an aralkyi group having one or more substituents bonded to a carbon atom in the ring, where one or more of the substituents contains a heteroatom, e.g., aralkyloxy described above, or groups such as
Figure imgf000010_0001
, where the denotes a point of attachment
[0038] The ligand may have general formula (ii) :
Figure imgf000010_0002
[0039] In general formula (ii), subscript x is an integer from 0 to 1 depending on the valency of Q1 . Q1 is selected from oxygen, sulphur, nitrogen and phosphorus.
[0040] In general formula (ii), A1 , A3, A4, A5, and A6 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A6 is not chlorobenzene.
[0041 ] In general formula (ii), A2 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group .
[0042] Alternatively, in general formula (ii), A2 and A3 may bond together to form a ring structure. Alternatively, A3 and A4 may bond together to form a ring structure.
Alternatively, A4 and A5 may bond together to form a ring structure. Alternatively, A5 and
A6 may bond together to form a ring structure. Such a ring structure is fused to the pyridine ring in general formula (ii).
[0043] Examples of ligands of general formula (ii) include 483, 484, 486, 488, 510, 512, 777, 785, 788, 799, 805, 819, 2363, 6269, 8838, 8842, 8856, 8945, and 8946 in Table 2.
[0044] Alternatively, the ligand may have general formula
Figure imgf000011_0001
[0045] In general formula (iii), Q2 is oxygen or sulphur.
[0046] In general formula (iii), A7, A8, A9, A1 0, and A1 2 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group.
[0047] In general formula (iii), A1 1 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that A1 1 is not benzyl.
[0048] Alternatively, in general formula (iii), A7 and A8 may combine to form a ring structure. Alternatively, A8 and A9 may combine to form a ring structure. Alternatively, A9 and A10 may combine to form a ring structure. Alternatively, A1 1 and A1 2 may combine to form a ring structure. Examples of ligands of general formula (iii) include 604, 2920, 2921 , 6886, 7282, 7377, and 10364 in Table 2.
[0049] Alternatively, the ligand may have general formula (iv) :
Figure imgf000011_0002
[0050] In general formula (iv), subscript x is an integer from 0 to 1 depending on the valency of Q3. Q3 is selected from oxygen, sulphur, and nitrogen.
[0051 ] In general formula (iv), A 5, A 6, A 7, A 8, A20, and A21 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group. [0052] In general formula (iv), each A1 9 is independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A19 does not contain diphenylphosphine.
[0053] Alternatively, in general formula (iv), A20 and A21 can be bonded together to form a ring structure. Alternatively, A1 9 and A1 8 can be bonded together to form a ring structure. Alternatively, A1 8 and A1 7 can be bonded together to form a ring structure.
Alternatively, A1 7 and A16 can be bonded together to form a ring structure. Alternatively,
A1 6 and A1 5 can be bonded together to form a ring structure. Examples of ligands of general formula (iv) include 755, 1430, 1483, 1832, 2072, 2915, 2927, 3472, 3586, 3746, 3749, 4098, 41 17, 5479, 6870, 7124, 7471 , 7496, 10132, and 10218 in Table 2.
[0054] Alternatively, the ligand may have general formula (v):
Figure imgf000012_0001
[0055] In general formula (v), subscript x is an integer from 0 to 1 depending on the valency of Q4 and whether Q4 to A29 is a single or double bond denoted by the dashed line. Subscript y is an integer from 0 to 1 depending on the valency of Q5, and whether Q5 to A31 is a single or double bond denoted by the dashed line.
[0056] In general formula (v), Q4 and Q5 are each independently selected from N, O, P, and S.
[0057] In general formula (v), A25, A26, A27, A28, A29, A30, A31 , and A32 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group.
[0058] Alternatively, in general formula (v), A29 and A25 may be bonded together to form a ring structure. Alternatively, A2^ and A2^ may be bonded together to form a ring structure. Alternatively, A2^ and A27 may be bonded together to form a ring structure.
Alternatively, A27 and A28 may be bonded together to form a ring structure. Alternatively, A28 and A32 may be bonded together to form a ring structure.
[0059] Alternatively, in general formula (v), A29 and A3^ may be bonded together to form a ring structure, with the proviso that the ring structure formed is not pyrrole. Alternatively, A31 and A^2 may be bonded together to form a ring structure, with the proviso that the ring structure formed is not pyrrole. Examples of ligands of general formula (v) include 165, 788, 799, 805, 819, 1 1 16, 1 125, 1214, 1547, 3544, 3547, 4151 , 4202, 7639, and 8749 in Table 2.
[0060] Alternatively, the ligand may have general formula (vi):
Figure imgf000013_0001
[0061] In general formula (vi), subscript x is an integer from 0 to 1 depending on the valency of Q8. Q8 is selected from N, O, P, and S.
[0062] In general formula (vi), A45, A46, A47, A49, A50, A51 , and A52 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that when Q8 is sulphur then A45 is not benzene.
[0063] In general formula (vi), A48 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group.
[0064] Alternatively, in general formula (vi), A4^ and A^2 may combine to form a ring structure. Alternatively, A^2 and may combine to form a ring structure. Alternatively, A^1 and A^0 may combine to form a ring structure. Alternatively, A^O and A49 may combine to form a ring structure. Alternatively, A4^ and A4^ may combine to form a ring structure. Examples of ligands of general formula (vi) include 635, 1249, 1888, 2061 , 2062, 2075, 2272, 3096, 3191 , 4202, 4990, 5177, 6253, 6322, 6340, 6372, 7124, and 7534.
[0065] Alternatively, the ligand may have general formula (vii):
Figure imgf000013_0002
[0066] In general formula (vii), subscript x is an integer from 0 to 1 depending on the valency of Q1 °. Q1 0 is selected from N, O, P, and S. A dashed line indicates single or double bond. [0067] In general formula (vii), A^6 and A^7 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group.
[0068] In general formula (vii), A^8 and A^5 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group.
[0069] Alternatively, in general formula (vii), A^6 and A^7 may combine to form a ring structure. Alternatively, A^5 and A^6 may combine to form a ring structure. Examples of ligands of general formula (vii) include ligands 732, 734, 735, 1936, 2956, 6417, 9042, and 10267 in Table 2.
ligand may have general formula (viii) :
Figure imgf000014_0001
[0071 ] In general formula (viii), subscript x is an integer from 0 to 1 depending on the valency of Q1 1 . Subscript y is an integer from 0 to 1 depending on the valency of Q1 2.
Q1 1 and Q1 2 are each independently selected from N, O, P, and S with the proviso that if Q1 1 or Q1 2 are nitrogen then they are not imine nitrogen. Dashed lines represent either single or double bonds.
[0072] In general formula (viii), A^O, A^1 , A^ and A66 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group.
[0073] In general formula (viii), each A62, each A63, and each A64 are independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group.
[0074] Alternatively, in general formula (viii), A^O and may be bonded together to form a ring structure. Alternatively, A^1 and A^2 may be bonded together to form a ring structure. Alternatively, A^2 and A 63 may be bonded together to form a ring structure. Alternatively, A63 and A^4 may be bonded together to form a ring structure. Alternatively, A^4 and A65 may be bonded together to form a ring structure. Alternatively, A65 and A66 may be bonded together to form a ring structure. Alternatively, A63 and A^1 may be bonded together to form a ring structure. Examples of ligands of general formula (viii) include 748, 1214, 1769, 3499, 3547, 3746, 3749, 6322, 6372, 7534, 8881 , 8977, 9042, and 9072 in Table 2.
[0075] Alternatively, the ligand may have general formula (ix) :
Figure imgf000015_0001
[0076] In general formula (ix), subscript x is an integer from 0 to 1 depending on the valency of Q1 7. Q1 7 is selected from N, O, P, and S. Q1 7 may alternatively be carbon with the proviso that when Q17 is carbon, the carbon forms a carbonyl bond with A81 and a hydroxyl group with A80 (for example ligand 2816). Q1 8 is selected from O and S. Q1 9 is selected from hydroxyl and thiol.
[0077] In general formula (ix), A82, A8^, A84, and A8^ are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group.
[0078] In general formula (ix), A8^ and A81 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group.
[0079] Alternatively, in general formula (ix), A81 and A82 may bond together to form a ring structure. Alternatively, A82 and A8^ may bond together to form a ring structure.
Alternatively, A8^ and A84 may bond together to form a ring structure. Alternatively, A84 and A85 may bond together to form a ring structure. Examples of ligands of general formula (ix) include ligands 2816, 3500, and 3505 in Table 2.
Figure imgf000015_0002
[0080] Alternatively, the ligand may have general formula (x):
[0081 ] In general formula (x), subscript x is an integer from 0 to 1 depending on the valency of Q1 6. Q1 6 is selected from N, O, P, and S. Q1 4 is selected from oxygen and sulphur. Q15 jS selected from hydroxyl and thiol.
[0082] In general formula (x), each A76 is independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group. [0083] In general formula (x), A77 and A78 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group.
[0084] In general formula (x), Alternatively, in general formula (x), A76 and A77 may bond together to form a ring structure. Alternatively, A77 and A78 may bond together to form a ring structure. Examples of ligands of general formula (x) include 2363, 2806, and 4226.
[0085] Alternatively, the ligand may have general formula (xi),
Figure imgf000016_0001
[0086] In general formula (xi), subscript x is an integer from 0 to 2 depending on the valency of Q50. Q50 is selected from N and C. Subscripts y and z are each independently an integer from 0 to 1 depending on the valency of the N that A90 and A88 are attached to, respectively. The dashed lines indicate single or double bonds. The two nitrogen atoms may be positively charged with a balancing negatively charged anion, alternatively chlorine or boron tetrafluoride
[0087] In general formula (xi), A86 and each A89 are each independently selected from a monovalent organic group, hydrogen, or an inorganic heteroatom containing group, with the proviso that A86 may not contain thiol or phenyl di-isopropyl.
[0088] In general formula (xi), A87 A88, A90, and A91 are each independently selected from a monovalent organic group, hydrogen, or an inorganic heteroatom containing group.
[0089] Alternatively, in general formula (xi), A88 and A90 may be bonded together to form a ring structure. Alternatively, A87 and A88 may be bonded together to form a ring structure. Alternatively, A87 and A86 may be bonded together to form a ring structure.
Alternatively, A86 and A91 may be bonded together to form a ring structure. Alternatively,
A91 and A90 may be bonded together to form a ring structure. Examples of ligands of general formula (xi) include 4226, 6253, 6340, 8500, 8538, 8749, 8881 , 8977, 9042, 10374, 10376, 10377, 10379, 10380, 10381 , 10390, 10450, 10451 , 10452, 10454, 10455, 10456, and 10457 in Table 2. [0090] Alternatively, the ligand may have general formula (xii)
Figure imgf000017_0001
[0091] In general formula (xii), subscript x is an integer from 1 to 5. Q20 is selected from N and P. Dashed lines indicate a single or double bond.
[0092] In general formula (xii), A90, A9 , A92, A93 A94, and A95 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that when Q20 is nitrogen and A95 is hydrogen then A9^ and A91 are not cyclohexyl, and with the proviso that A90 and A91 are not be di(tert-butyl) phenol.
[0093] Alternatively, A90 and A91 may be bonded together to form a ring structure, with the proviso that when the ring is a phosphalane ring, then A92 and A93 form a phenyl group. Alternatively, A91 and A92 may be bonded together to form a ring structure.
Alternatively, A92 and A93 may be bonded together to form a ring structure with the proviso that when Q2^ is nitrogen then the ring structure is not indene. Alternatively, A93 and A94 may be bonded together to form a ring structure with the proviso that when Q20 is nitrogen then there are no other hetero-atoms in the ring structure with Q2^. Alternatively,
A94 and A95 may be bonded together to form a ring structure.
[0094] In general formula (xii), when subscript x is 2 or more, then two or more instances of A93 may bond together to form a ring structure. Examples of ligands of general formula (xii) include ligands 10383, 10384, 10385, 10386, 10387, 10389, 10391 , 10392, 10394, 10397, 10398, 10399, 10400, 10401 , 10404, 10407, and 10447 in Table 2.
[0095] Altern ral formula (xiii):
Figure imgf000017_0002
[0096] In general formula (xiii), subscript x is an integer from 0 to 1 depending on the valency of Q21 . Q21 is selected from N, O, P, and S. [0097] In general formula (xiii), A96, A97, A98, A99, A100, A 01 , A102, A103, a104, A105, A106j A"! 07, and A108 are eacn independently selected from a monovalent organic group, hydrogen, a halogen, and an inorganic heteroatom containing group. Alternatively, A96 and A97 may bond together to form a ring structure. Alternatively, A99 and A100 may bond together to form a ring structure. Alternatively, Ag6 and A1 °8 may bond together to form a ring structure. Alternatively, A108 and A10 may bond together to form a ring structure. Alternatively, A1 °7 and A1 °6 may bond together to form a ring structure.
Alternatively, A106 and A105 may bond together to form a ring structure. Alternatively, A105 and A1 °4 may bond together to form a ring structure, with the proviso that the bridging atom is not N in an amine group. Alternatively, A104 and A103 may bond together to form a ring structure. Alternatively, A103 and A102 may bond together to form a ring structure. Alternatively, A1 °2 and A1 °1 may bond together to form a ring structure.
Examples of ligands of general formula (xiii) include 10403, 10405, 10406, and 10446 in Table 1 .
ve general formula (xiv):
Figure imgf000018_0001
[0099] In general formula (xiv), subscripts x and y are each independently an integer from 0 to 5. A11 1 , A110, and A1 12 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group. Examples of ligands of general formula (xiv) include 3179 in Table 2.
[0100] Alternatively, the ligand may have general formula (xv):
Figure imgf000018_0002
[0101 ] In general formula (xv), Q22 and Q23 are each independently selected from oxygen and sulphur. A1 15, A1 16, A117, and A118 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group. Alternatively, A1 16 and A1 15 may combine to form a ring structure. Alternatively, A1 1 8 and A1 1 9 may combine to form a ring structure. Examples of ligands of general formula
(xv) include ligands 4570 and 8768 in Table 2.
[ may have general formula (xvi):
Figure imgf000019_0001
[0103] In general formula (xvi), subscripts x and y are each independently integers from
0 to 4. Q24 and Q25 are each independently selected from O and S. Subscript z is an integer from 0 to 1 .
[0104] In general formula (xvi), each A1 2^ is independently selected from a monovalent organic group, hydrogen, halogen, and inorganic heteroatom containing group.
[0105] In general formula (xvi), A1 21 and A1 22 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group. Examples of ligands of general formula (xvi) include 4548 and 6510 in Table 2.
[0106] Alternatively, the ligand may have general formula (xvii):
Figure imgf000019_0002
In general formula (xvii), Q26 is selected from O and S. Q27 is selected from N and C. Subscript x is an integer from 0 to 4. A 5, A 6, A 7, A 8, and A 30 are each independently selected from a monovalent organic group, hydrogen, a halogen, or an inorganic heteroatom containing group. A1 29 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group, with the proviso that A1 28 and A129 may combine to form a ring structure. Examples of ligands of general formula (xvii) include 10441 , 10444, and 10445 in Table 2. [0107] Alternatively, the ligand may have general formula (xviii):
Figure imgf000020_0001
[0108] In general formula (xviii), A132j A133j anc| A134 are each independently selected from a monovalent organic group, hydrogen, a halogen, or an inorganic heteroatom containing group.
[0109] In general formula (xviii), A131 and A135 are independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group. Examples of ligands of general formula (xviii) include 10453 in Table 2.
[0110] Alternatively, the ligand may have general formula (xix):
Figure imgf000020_0002
[0111] In general formula (xix), each A1 41 , each A1 42, each A1 43, and each A1 44 are independently selected from a monovalent organic group, hydrogen, halogen, or inorganic group.
[0112] In general formula (xix), A136j A13 j A139j anc: A140 are independently selected from a monovalent organic group, hydrogen, or an inorganic group. Examples of ligands of general formula (xix) include 10150 in Table 2.
[0113] The neutral forms of exemplary ligands are shown in Table 2. Alternatively, the ligand used to prepare ingredient (A) may be a ligand selected from the group consisting of the ligands in Table 2
Figure imgf000020_0003
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001

Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001

Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
[0114] Various ligands useful herein and in the tables above are commercially available {e.g., from vendors such as American Custom Chemical Corporation of San Diego, California, U.S.A., Alfa Aesar of Ward Hill, Massachusetts, U.S.A., Ambinter of Paris, France, Anthem Pharmaceutical Research LLC of Newington, Connecticut, U.S.A., ChemBridge Corporation of San Diego, California, U.S.A., Combi-Blocks of San Diego, California, U.S.A., Gelest, Inc. of Morrisville, Pennsylvania, U.S.A., Interchim, Inc. of San Pedro, California, U.S.A., Maybridge Chemical Co., Ltd. of Belgium, Princeton
Biomolecular Research, Inc. of Princeton, New Jersey, U.S.A., Sigma-Aldrich, Inc. of St. Louis, Missouri, U.S.A., Strem Chemicals, Inc. of Newburyport, Massachusetts, U.S.A., TCI America of Portland, Oregon, U.S.A., and from VWR International, LLC, of Radnor, Pennsylvania, U.S.A.) and/or can be prepared using conventional synthetic methods in organic chemistry.
[0115] Ingredient (A) may be prepared by a method comprising combining a ligand and a Ni precursor, described above. The method may optionally further comprise a step of dissolving either the Ni precursor, or the ligand, or both, in a solvent before combining the Ni precursor and the ligand. Suitable solvents are exemplified by those described below for ingredient (S). Alternatively, the ligand may be dissolved in a solvent in a container, and the solvent may thereafter be removed before adding the Ni precursor to the container with the ligand. The amounts of ligand and Ni precursor are selected such that the mole ratio of ligand to Ni precursor (Metal: Ligand Ratio) may range from 10:1 to 1 :10, alternatively 2:1 to 1 :2, alternatively 1 :1 to 1 :4, and alternatively 1 :1 to 1 :2. Combining the Ni precursor and the ligand may be performed by any convenient means, such as mixing them together in or shaking the container.
[0116] Reacting the Ni precursor and ligand may be performed by under any convenient conditions such as allowing the Ni precursor and ligand prepared as described above to react at -80 °C to 200 °C, alternatively room temperature (RT) of 25 Ό for a period of time, by heating, or a combination thereof. Heating may be performed at, for example greater than 25 °C to 200 °C, alternatively greater than 25 °C to 75 °C. Heating may be performed by any convenient means, such as via a heating mantle, heating coil, or placing the container in an oven. The complexation reaction temperature depends on various factors including the reactivities of the specific Ni precursor and ligand selected and the Metal : Ligand Ratio, however, temperature may range from 25 °C to 200 °C, alternatively 25 °C to 75 °C. Complexation reaction time depends on various factors including the reaction temperature selected, however, complexation reaction time may typically range from 1 second (s) to 48 hours (h), alternatively 1 minute (min) to 30 hours (h), and alternatively 45 min to 15 h. The ligand and Ni precursor may be combined and heated sequentially. Alternatively, the ligand and Ni precursor may be combined and heated concurrently.
[0117] The method of preparing the catalytically active reaction product of ingredient (A) may further comprise activating the reaction product prepared as described above.
Activating the reaction product can be performed by reducing the formal oxidation state of the metal atom in the Ni-ligand complex by combining the reaction product described above with a reducing agent. Examples of reducing agents that may be combined with the reaction product include an alkalimetal amalgam ; hydrogen, a metal hydride such as lithium aluminum hydride (UAIH4) or sodium naphthalenide; a silyl hydride (which may be in addition to, or instead of, all or a portion of a silane crosslinker, described below); or a metal borohydride such as sodium triethylborohydride (NaEt3BH), lithium
triethylborohydride (LiEt^BH), or sodium borohydride (NaBH^. Suitable reducing agents include those described in Chem. Rev. 1996, 96, 877-910.
[0118] Alternatively, the reaction product described above can be activated by a process comprising combining the reaction product described above with an ionic activator.
Examples of ionic activators for use in this process include carboranes, such as
Li+[CB-| λ H6Br6]-, Li+[CB9H5Br5]-, Li+[CB-| λ Y\- 0Br2]-, and Li+[CB9H8Br2]-, NH^ICBu HeBre]-, NH4+[CB9H5Br5]-, NH^ICBu H^Br^-, NH4+[CB9H8Br2]-,
Na+[CB-| 1 H6Br6]-, Na+[CB9H5Br5]-, Na+[CB-| 1 H-| 0Br2]-, and Na+[CB9H8Br2]-; or metal borates such as lithium tetrakis(pentafluorophenyl)borate (LiBArF), lithium tetrakis(3,5- trifluoromethyl)phenylborate, sodium tetrakis(3,5-trifluoromethyl)phenylborate, or a mixture thereof.
[0119] Alternatively, the reduction product described above can be activated by a method comprising combining the reaction product described above with a neutral activator.
Examples of neutral activators for use in this method include tris(pentafluorophenyl)borane and tris(pentafluorophenyl)allane.
[0120] The method of preparing the catalytically active reaction product of ingredient (A) may optionally further comprise adding a solvent after the reaction. Suitable solvents are exemplified by those described below for ingredient (S). Alternatively, the method may optionally further comprise removing a reaction by-product and/or the solvent, if the solvent is present ( e.g., used to facilitate combination of the Ni precursor and the ligand before or during the complexation reaction. By-products include, for example, H-A (where A is as defined above in general formula (i)) or any species resulting from reacting a displaceable substituent off the Ni precursor when the ligand reacts with the Ni precursor. By-products may be removed by any convenient means, such as stripping or distillation, with heating or under vacuum, and/or filtration, crystallization, or a combination thereof. The resulting isolated Ni-ligand complex may be used as the catalytically active reaction product of ingredient (A).
[0121 ] Alternatively, the reaction by-products are not removed before using the catalytically active reaction product as ingredient (A). For example, the ligand and Ni precursor may be reacted as described above, with or without solvent removal, and with or without activation, and the resulting reaction product (comprising the Ni-ligand complex and the reaction by-product and optionally a solvent or diluent) may be used as ingredient (A). Without wishing to be bound by theory, it is thought that a by-product may act as a hydrosilylation reaction catalyst, or as a co-catalyst or an activator, in addition to the Ni- ligand complex. Therefore, the reaction product may catalyze a hydrosilylation reaction.
[0122] The composition may contain one single catalyst. Alternatively, the composition may comprise two or more catalysts described above as ingredient (A), where the two or more catalysts differ in at least one property such as selection of ligand, selection of precursor, Metal: Ligand Ratio, and definitions for group A in general formula (i). The composition may be free of platinum catalysts. Alternatively, the composition may be free of conventional metal catalysts. Alternatively, the composition may be free of any Ni compound that would catalyze the hydrosilylation reaction of the unsaturated groups on ingredient (B) other than the ingredient (A). Alternatively, the composition may be free of hydrosilylation reaction catalysts other than ingredient (A). Alternatively, the composition may be free of any ingredient that would catalyze the hydrosilylation reaction of the unsaturated groups on ingredient (B) other than ingredient (A).
[0123] Ingredient (A) is present in the composition in a catalytically effective amount. The exact amount depends on various factors including reactivity of ingredient (A), the type and amount of ingredient (B), and the type and amount of any additional ingredient, if present. However, the amount of ingredient (A) in the composition may range from 1 part per million (ppm) to 5 %, alternatively 0.1 % to 2 %, and alternatively 1 ppm to 1 %, based on total weight of all ingredients in the composition.
[0124] Ingredient (B) is an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction. Alternatively, ingredient (B) may have an average of two or more aliphatically unsaturated organic groups per molecule. The aliphatically unsaturated organic groups may be alkenyl exemplified by, but not limited to, vinyl, allyl, propenyl, butenyl, and hexenyl. The unsaturated organic groups may be alkynyl groups exemplified by, but not limited to, ethynyl, propynyl, and butynyl.
[0125] Ingredient (B) of the composition may be an unsaturated hydrocarbon, where the unsaturated group is capable of reacting via hydrosilylation reaction. Ingredient (B) may be monomeric. For example, suitable aliphatically unsaturated organic compounds for ingredient (B) include, but are not limited to alkenes such as ethylene, propene, 1 -butene, 2-butene, 1 -pentene, 1 -hexene, 1 -heptene; halogenated alkenes, such as allyl chloride; diolefins such as divinylbenzene, butadiene, 1 ,5-hexadiene, and 1 -buten-3-yne;
cycloolefins such as cyclohexene and cycloheptene; and alkynes such as acetylene, propyne, and 1 -hexyne.
[0126] Oxygen-containing aliphatically unsaturated compounds can also be used for ingredient (B), for example, where the unsaturation is ethylenic, such as vinylcyclohexyl epoxide, allyl glycidyl ether, methylvinyl ether, divinylether, phenylvinyl ether, monoallyl ether of ethylene glycol, allyl aldehyde, methylvinyl ketone, phenylvinyl ketone, acrylic acid, methacrylic acid, methyl acrylate, allyl acrylate, methyl methacrylate, allyl methacrylate, vinylacetic acid, vinyl acetate, and linolenic acid.
[0127] Heterocyclic compounds containing aliphatic unsaturation in the ring, such as dihydrofuran, and dihydropyran, are also suitable as ingredient (B). Unsaturated compounds containing nitrogen substituents such as acrylonitrile, N-vinylpyrrolidone, alkyl cyanide, nitroethylene are also suitable as ingredient (B). [0128] Alternatively, ingredient (B) of the composition comprise a polymer. Ingredient (B) may comprise a base polymer having an average of one or more aliphatically unsaturated organic groups, capable of undergoing a hydrosilylation reaction, per molecule. Ingredient (B) may comprise a polymer (e.g., copolymers or terpolymers) of the various compounds described above, provided there is at least one aliphatic unsaturation capable of undergoing a hydrosilylation reaction. Examples include polymers derived from olefinic monomers having 2 to 20 carbon atoms and dienes having 4 to 20 carbon atoms; polymers of monoolefin, isomonoolefin and vinyl aromatic monomers, such as monoolefins having 2 to 20 carbon groups, isomonoolefins having 4 to 20 carbon groups, and vinyl aromatic monomers including styrene, para-alkylstyrene, para-methylstyrene. Alternatively, the compounds can be poly(dienes). Most polymers derived from dienes usually contain unsaturated ethylenic units on backbone or side-chains. Representative examples include polybutadiene, polyisoprene, polybutenylene, poly(alkyl-butenylene) where alkyl includes alkyl groups having 1 to 20 carbon atoms, poly(phenyl-butenylene), polypentenylene, natural rubber (a form of polyisoprene); and butyl rubber (copolymer of isobutylene and isoprene).
[0129] Alternatively, ingredient (B) may comprise a halogenated olefin polymer having aliphatic unsaturation. Representative examples of a halogenated olefin polymer having aliphatic unsaturation include polymers resulting from the bromination of a copolymer of isomonoolefin with para-methylstyrene to introduce benzylic halogen, halogenated polybutadienes, halogenated polyisobutylene, poly(2-chloro-1 ,3-butadiene),
polychloroprene (85% trans), poly(1 -chloro-1 -butenylene) (Neoprene®), and
chlorosulfonated polyethylene.
[0130] Alternatively, ingredient (B) may comprise polymers containing other compounds described above such as vinyl ether groups, acrylate groups, methyacrylate groups, and epoxy-functional groups.
[0131 ] Alternatively, ingredient (B) may comprise a silane having aliphatic unsaturation. Alternatively the silane may have a general formula of R35xxSiR36(4-xx) where subscript xx is an integer from 1 to 4, alternatively 1 to 3, and alternatively 1 . R35 is an aliphatically unsaturaged organic group, and R36 is selected from H, a halogen atom , and aa monovalent organic group.
[0132] Alternatively, ingredient (B) may comprise a silicon containing base polymer having a linear, branched, cyclic, or resinous structure having aliphatic unsaturation.
Alternatively, the base polymer may have a linear and/or branched structure. Alternatively, the base polymer may have a resinous structure. The base polymer may be a homopolymer or a copolymer. Ingredient (B) may be one base polymer. Alternatively, ingredient (B) may comprise two or more base polymers differing in at least one of the following properties: structure, viscosity, average molecular weight, siloxane units, and sequence. The aliphatically unsaturated organic groups in the base polymer may be located at terminal, pendant, or both terminal and pendant positions.
[0133] The remaining silicon-bonded organic groups in the base polymer for ingredient (B) may be monovalent organic groups free of aliphatic unsaturation. Examples of monovalent hydrocarbon groups include, but are not limited to, alkyl such as Me, Et, Pr, Bu, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl; cycloalkyl such as cyclopentyl and cyclohexyl; aryl such as Ph, tolyl, xylyl, and naphthyl; and aralkyl such as benzyl, 1 -phenylethyl and 2-phenylethyl. Examples of monovalent halogenated hydrocarbon groups include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl groups; fluorinated alkyl groups such as fluoromethyl, 2- fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl,
5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7- pentafluorooctyl; chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl, 2,3- dichlorocyclopentyl; and fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3- difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl. Examples of other monovalent organic groups include, but are not limited to, hydrocarbon groups substituted with oxygen atoms such as glycidoxyalkyi, and hydrocarbon groups substituted with nitrogen atoms such as aminoalkyl and cyano-functional groups such as cyanoethyl and cyanopropyl.
[0134] Ingredient (B) may comprise a polydiorganosiloxane of
Formula (I): R12R2SiO(R12SiO)a(R1 R2SiO) SiR1 2R2,
Formula (II): R1 3SiO(R1 2SiO)c(R1 R2SiO)dSiR1 3,
or a combination thereof.
[0135] In formulae (I) and (II), each R1 is independently a hydrogen atom or a monovalent organic group free of aliphatic unsaturation and each R2 is independently an aliphatically unsaturated organic group, exemplified by those described above. Subscript a may be 0 or a positive number. Alternatively, subscript a has an average value of at least 2. Alternatively subscript a may have a value ranging from 2 to 2000. Subscript b may be 0 or a positive number. Alternatively, subscript b may have an average value ranging from 0 to 2000. Subscript c may be 0 or a positive number. Alternatively, subscript c may have an average value ranging from 0 to 2000. Subscript d has an average value of at least 2. Alternatively subscript d may have an average value ranging from 2 to 2000. Suitable monovalent organic groups for R1 are as described above for ingredient (B). Alternatively, each R1 is a monovalent hydrocarbon group exemplified by alkyl such as Me and aryl such as Ph. Each R2 is independently an aliphatically unsaturated monovalent organic group as described above for ingredient (B). Alternatively, R2 is exemplified by alkenyl groups such as vinyl, allyl, butenyl, and hexenyl; and alkynyl groups such as ethynyl and propynyl.
[0136] Ingredient (B) may comprise a polydiorganosiloxane such as
i) dimethylvinylsiloxy-terminated polydimethylsiloxane,
ii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylvinylsiloxane),
iii) dimethylvinylsiloxy-terminated polymethylvinylsiloxane,
iv) trimethylsiloxy-terminated poly(dimethylsiloxane/methylvinylsiloxane),
v) trimethylsiloxy-terminated polymethylvinylsiloxane,
vi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylvinylsiloxane),
vii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylphenylsiloxane), viii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/diphenylsiloxane),
ix) phenyl, methyl,vinyl-siloxy-terminated polydimethylsiloxane,
x) dimethylhexenylsiloxy-terminated polydimethylsiloxane,
xi) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane/methylhexenylsiloxane), xii) dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane,
xiii) trimethylsiloxy-terminated poly(dimethylsiloxane/methylhexenylsiloxane),
xiv) trimethylsiloxy-terminated polymethylhexenylsiloxane
xv) dimethylhexenyl-siloxy terminated poly(dimethylsiloxane/methylhexenylsiloxane), xvi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylhexenylsiloxane) xvii) a combination thereof.
[0137] Methods of preparing polydiorganosiloxane fluids suitable for use as ingredient (B), such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes, are well known in the art.
[0138] In addition to, or instead of, the polydiorganosiloxane described above, ingredient
(B) may further comprise a resin such as an MQ resin consisting essentially of R33SiO-|/2 units and S1O4/2 units, a TD resin consisting essentially of R3SiC>3/2 units and R32SiC>2/2 units, an MT resin consisting essentially of R33SiO-|/2 units and R3SiC>3/2 units, an MTD resin consisting essentially of R33SiO-| /2 units, R3SiC>3/2 units, and R32SiC>2/2 units, or a combination thereof. [0139] Each R3 is a monovalent organic group exemplified by those described above for ingredient (B). Alternatively, the monovalent organic groups represented by R3 may have
1 to 20 carbon atoms. Alternatively, examples of monovalent organic groups for R3 include, but are not limited to, monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups.
[0140] The resin may contain an average of 3 to 30 mole percent of aliphatically unsaturated organic groups, alternatively 0.1 to 30 mole percent, alternatively 0.1 to 5 mole percent, alternatively 3 to 100 mole percent. The aliphatically unsaturated organic groups may be alkenyl groups, alkynyl groups, or a combination thereof. The mole percent of aliphatically unsaturated organic groups in the resin is the ratio of the number of moles of unsaturated group-containing siloxane units in the resin to the total number of moles of siloxane units in the resin, multiplied by 100.
[0141] Methods of preparing resins are well known in the art. For example, resin may be prepared by treating a resin copolymer produced by the silica hydrosol capping process of Daudt, et al. with at least an alkenyl-containing endblocking reagent. The method of Daudt et ai, is disclosed in U.S. Patent 2,676,182.
[0142] The method of Daudt, et al. involves reacting a silica hydrosol under acidic conditions with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or mixtures thereof, and recovering a copolymer having M- units and Q-units. The resulting copolymers generally contain from 2 to 5 percent by weight of hydroxyl groups.
[0143] The resin, which typically contains less than 2 % of silicon-bonded hydroxyl groups, may be prepared by reacting the product of Daudt, et al. with an unsaturated organic group-containing endblocking agent and an endblocking agent free of aliphatic unsaturation, in an amount sufficient to provide from 3 to 30 mole percent of unsaturated organic groups in the final product. Examples of endblocking agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable endblocking agents are known in the art and exemplified in U.S. Patents 4,584,355; 4,591 ,622; and 4,585,836. A single endblocking agent or a mixture of such agents may be used to prepare the resin.
[0144] Alternatively, ingredient (B) may comprise a silicon containing base polymer other than the polyorganosiloxanes described above. For example, other compounds suitable for ingredient (B) include silazanes and/or polymeric materials containing silicon atoms joined together by hydrocarbyl groups such as alkylene or polyalkylene groups or arylene groups. The silicon-modified organic compounds useful as ingredient (B) include organic polymers having at least one silicon atom attached as a silane or a siloxane segment. The silicon-containing units can contain aliphatic unsaturation and can be attached at the terminal and/or pendant positions on the organic polymer chain or as a copolymer. Other representative silicon-modified organic polymers for ingredient (B) are exemplified by, but not limited to alkenylsiloxy-functional polymers such as vinylsiloxy-, allylsiloxy-, and hexenylsiloxy- organic polymers and siloxane-organic block copolymers. Examples of silane-modified organic polymers are silylated polymers derived from olefins,
isomonoolefin, dienes, ethylene or propylene oxides, and vinyl aromatic monomers having 2 to 20 carbon atoms such as the silane-grafted copolymers of isomonoolefin and vinyl aromatic monomers.
[0145] Examples of silicon-modified organic polymers described by above include vinylsiloxy-terminated or hexenylsiloxy-terminated poly(dimethylsiloxane/hydrocarbyl) copolymers, vinylsiloxy-terminated or hexenylsiloxy-terminated
poly(dimethylsiloxane/polyoxyalkylene) block copolymers, alkenyloxydimethylsiloxy- terminated polyisobutylene and alkenyloxydimethylsiloxy-terminated
polydimethylsiloxane/polyisobutylene block copolymers. Examples of suitable compounds for ingredient (B) may be found, for example, in WO 2003/093369.
[0146] The amount of ingredient (B) in the composition depends on various factors including the desired form of the reaction product of the composition, the quantity and hydrosilylation reactivity of the aliphatically unsaturated groups of ingredient (B), the type and amount of ingredient (A), and the content of silicon bonded hydrogen atoms of, ingredient (B) and/or ingredient (C). However, the amount of ingredient (B) may range from 0.1 % to 99.9 % based on the weight of all ingredients in the composition.
[0147] Ingredient (C) in the composition is a SiH functional compound, i.e., a compound having an average, per molecule, of one or more silicon bonded hydrogen atoms.
Ingredient (C) may comprise a silane and/or an organohydrogensilicon compound.
Alternatively, ingredient (C) may have an average, per molecule, of at least two silicon- bonded hydrogen atoms. The amount of ingredient (C) in the composition depends on various factors including the SiH content of ingredient (C), the unsaturated group content of ingredient (B), and the properties of the reaction product of the composition desired, however, the amount of ingredient (C) may be sufficient to provide a molar ratio of SiH groups in ingredient (C) to aliphatically unsaturated organic groups in ingredient (B) (commonly referred to as the SiH:Vi ratio) ranging from 0.3:1 to 5:1 , alternatively 0.1 :10 to 10:1. Ingredient (C) can have a monomeric or polymeric structure. When ingredient (C) has a polymeric structure, the polymeric structure may be linear, branched, cyclic, or resinous structure. When ingredient (C) is polymeric, then ingredient (C) can be a homopolymer or a copolymer. The silicon-bonded hydrogen atoms in ingredient (C) can be located at terminal, pendant, or at both terminal and pendant positions. Ingredient (C) may be one SiH functional compound. Alternatively, ingredient (C) may comprise a combination of two or more SiH functional compounds. Ingredient (C) may be two or more organohydrogenpolysiloxanes that differ in at least one of the following properties:
structure, average molecular weight, viscosity, siloxane units, and sequence.
[0148] Ingredient (C) may comprise a silane of formula R4 eSiHf, where subscript e is 0,
1 , 2, or 3; subscript f is 1 , 2, 3, or 4, with the proviso that a sum of (e + f) is 4. Each R4 is independently a halogen atom or a monovalent organic group. Suitable halogen atoms for
R4 are exemplified by chlorine, fluorine, bromine, and iodine; alternatively chlorine.
Suitable monovalent organic groups for R4 include, but are not limited to, monovalent hydrocarbon and monovalent halogenated hydrocarbon groups. Monovalent hydrocarbon groups include, but are not limited to, alkyl such Me, Et, Pr, Bu, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl; cycloalkyi such as cyclopentyl and cyclohexyl; aryl such as Ph, tolyl, xylyl, and naphthyl; and aralkyl such as benzyl, 1 -phenylethyl and 2- phenylethyl. Examples of monovalent halogenated hydrocarbon groups include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl groups; fluorinated alkyl groups such as fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4- trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3- nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl; chlorinated cycloalkyi groups such as 2,2- dichlorocyclopropyl, 2,3-dichlorocyclopentyl; and fluorinated cycloalkyi groups such as 2,2- difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5- methylcycloheptyl. Examples of other monovalent organic groups include, but are not limited to, hydrocarbon groups substituted with oxygen atoms such as glycidoxyalkyl, and alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy; and hydrocarbon groups substituted with nitrogen atoms such as aminoalkyl and cyano-functional groups such as cyanoethyl and cyanopropyl. Examples of suitable silanes for ingredient (C) are exemplified by trichlorosilane (HSiCl3), Me2HSiCI, or MeHSi(OMe)2- [0149] Alternatively, the organohydrogensilicon compound of ingredient (C) may comprise a polyorganohydrogensiloxane comprising siloxane units including, but not limited to, HR5 2SiO-|/2, R53SiO-|/2, HR5SiC>2/2, R52SiC>2/2, R5SiC>3/2, HS1O3/2 and S1O4/2 units. In the preceding formulae, each R5 is independently selected from the monovalent organic groups free of aliphatic unsaturation described above.
[0150] Ingredient (C) may comprise a polyorganohydrogensiloxane of
Formula (III): R5 3SiO(R52SiO)g(R5HSiO)hSiR5 3, Formula (IV): R¾HSiO(R¾SiO)j(R5HSiO)jSiR52H, or
a combination thereof.
[0151 ] In formulae (III) and (IV) above, subscript g has an average value ranging from 0 to 2000, subscript h has an average value ranging from 2 to 2000, subscript i has an average value ranging from 0 to 2000, and subscript j has an average value ranging from 0 to 2000. Each R5 is independently a monovalent organic group, as described above.
[0152] Polyorganohydrogensiloxanes for ingredient (C) are exemplified by:
a) dimethylhydrogensiloxy-terminated polydimethylsiloxane,
b) dimethylhydrogensiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane), c) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane,
d) trimethylsiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane),
e) trimethylsiloxy-terminated polymethylhydrogensiloxane,
f) a resin consisting essentially of H(CH3)2SiO-| /2 units and S1O4/2 units, and
g) a combination thereof.
[0153] Methods of preparing linear, branched, and cyclic organohydrogenpolysiloxanes suitable for use as ingredient (C), such as hydrolysis and condensation of
organohalosilanes, are well known in the art. Methods of preparing
organohydrogenpolysiloxane resins suitable for use as ingredient (C) are also well known as exemplified in U.S. Patents 5,310,843; 4,370,358; and 4,707,531 .
[0154] Alternatively, the organohydrogensilicon compound of ingredient (C) may com rise a compound of formula (V) :
Figure imgf000049_0001
where each R29 is independently selected from a hydrogen atom and a monovalent organic group comprising 1 to 20 member atoms, subscript k is an integer with a value ranging from 4- 0 to 18, subscript m is an integer with a value ranging from 0 2 to 19, k + m is an integer with a value ranging from 3 to 20, alternatively 3 to 40. Each R30 is independently selected from a monovalent organic group a halogen atom or a siloxane unit as described in the sections above. Alternatively each R30 is a functional group independently selected from a halogen atom, an ether group, an alkoxy group, an alkoxyether group, an acyl group, an epoxy group, an amino group, a silyl group, or a -Z- R31 group, where each Z is independently selected from an oxygen atom and a divalent hydrocarbon group comprising 2 to 20 carbon atoms, each R31 group is independently selected from -BR29 U R322-u> -Si R29 v R323-v, or a group described by formula (VI) : (R323-nR29nSi01 /2)w(R322-oR29oSi02/2)x(R32i -p
R29pSi03/2)y(Si04/2)z(CR29 qR32 1 -q)aa(CR29rR322-r)bb(0(CR29sR322
s)cc(CR29 tR32 3-t)dd
where B refers to boron, each R29 is as described above, the sum of
w+x+y+z+aa+bb+cc+dd is at least 2, subscript n is an integer with a value ranging from 0 to 3, subscript o is an integer with a value ranging from 0 to 2, subscript p is an integer with a value ranging from 0 to 1 , subscript q is an integer with a value ranging from 0 to 1 , subscript r is an integer with a value ranging from 0 to 2, subscript s is an integer with a value ranging from 0 to 2, subscript t is an integer with a value ranging from 0 to 3, subscript u is an integer with a value ranging from 0 to 2, subscript v is an integer with a value ranging from 0 to 3, each R32 is a functional group independently selected from a halogen atom , an ether group, an alkoxy group, an alkoxyether group, an acyl group, an epoxy group, an amino group, a silyl group, or a Z-G group, where Z is as described above each G is a cyclosiloxane described by formula (VII):
Figure imgf000050_0001
where R29 and R30 are as described above, subscript ee is 1 , subscript ff is an integer with a value ranging from 0 to 18, subscript gg is an integer with a value ranging from 0 to 18, ff+gg is an integer with a value ranging from 2 to 20, provided in formula (VII) that one of the R32 groups is replaced by the Z group bonding the R31 group to the cyclosiloxane of formula (VII), and provided further if aa+bb+cc+dd>0 then w+x+y+z>0.
[0155] Such organohydrogensilicon compounds are commercially available and include, SYL-OFF® SL2 CROSSLINKER and SYL-OFF® SL12 CROSSLINKER, both of which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A. The organohydrogensilicon compounds described above and methods for their preparation are exemplified in WO2003/093349 and WO2003/093369. An exemplary
organohydrogensilicon compound may have the general formula:
Figure imgf000051_0001
, where each R33 is independently selected from a hydrogen atom and a monovalent organic group; each R34 is independently selected from a hydrogen atom, a monovalent organic
Figure imgf000051_0002
group, and a group of formula ; subscript hh is an integer with a value of at least 1 ; subscript jj is an integer with a value of at least 1 ; and subscript ii is an integer with a minimum value of 0. In the general formula, at least one instance of R33 is a hydrogen atom. Suitable monovalent organic groups for R33 and/or
R34 are exemplified by those groups described above for R29.
[0156] The exact amount of ingredient (C) in the composition depends on various factors including reactivity of ingredient (A), the type and amount of ingredient (B), whether ingredient (B) contains a silicon bonded hydrogen atom, and the type and amount of any additional ingredient (other than ingredient (C)), if present. However, the amount of ingredient (C) in the composition may range from 0 % to 25 %, alternatively 0.1 % to 15 %, and alternatively 1 % to 5 %, based on total weight of all ingredients in the composition.
[0157] Ingredient (D) is a spacer. Spacers can comprise organic particles, inorganic particles, or a combination thereof. Spacers can be thermally conductive, electrically conductive, or both. Spacers can have a desired particle size, for example, particle size may range from 25 micrometers (μιη) to 125 μιη. Spacers can comprise monodisperse beads, such as glass or polymer (e.g., polystyrene) beads. Spacers can comprise thermally conductive fillers such as alumina, aluminum nitride, atomized metal powders, boron nitride, copper, and silver. The amount of ingredient (D) depends on various factors including the particle size distribution, pressure to be applied during use of the composition or the cured product prepared therefrom , temperature during use, and desired thickness of the composition or the cured product prepared therefrom . However, the composition may contain an amount of ingredient (D) ranging from 0.05 % to 2 %, alternatively 0.1 % to 1 %.
[0158] Ingredient (E) is an extender and/or a plasticizer. An extender comprising a nonfunctional polyorganosiloxane may be used in the composition. For example, the non- functional polyorganosiloxane may comprise difunctional units of the formula R62Si02/2 and terminal units of the formula R73SiR28-, where each R^ and each R7 are
independently a monovalent organic group such as a monovalent hydrocarbon group exemplified by alkyl such as methyl, ethyl, propyl, and butyl; alkenyl such as vinyl, allyl, and hexenyl; aryl such as Ph, tolyl, xylyl, and naphthyl; and aralkyl groups such as phenylethyl; and R28 is an oxygen atom or a divalent group linking the silicon atom of the terminal unit with another silicon atom. The divalent linking group for R28 may be a divalent organic group, a silicone organic group, or a combination of a divalent hydrocarbon group and a divalent siloxane group. Alternatively, each R28 may be independently selected from an oxygen atom and a divalent hydrocarbon group. Alternatively, each R28 may be an oxygen atom . Alternatively, each R28 may be a divalent hydrocarbon group exemplified by an alkylene group such as ethylene, propylene, butylene, or hexylene; an arylene group such as phenylene, or an alkylarylene group such as:
Figure imgf000052_0001
. Alternatively, an instance of R28 may be an oxygen atom while a different instance of R28 is a divalent hydrocarbon group. Non-functional polyorganosiloxanes are known in the art and are commercially available. Suitable non-functional polyorganosiloxanes are exemplified by, but not limited to, polydimethylsiloxanes. Such polydimethylsiloxanes include DOW CORN ING® 200 Fluids, which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A. and may have viscosity ranging from 50 cSt to 1 00,000 cSt, alternatively 50 cSt to 50,000 cSt, and alternatively 12,500 cSt to 60,000 cSt. [0159] An organic plasticizer may be used in addition to, or instead of, the non-functional polyorganosiloxane extender described above. Organic plasticizers are known in the art and are commercially available. The organic plasticizer may comprise a phthalate, a carboxylate, a carboxylic acid ester, an adipate or a combination thereof. The organic plasticizer may be selected from the group consisting of: bis(2-ethylhexyl) terephthalate; bis(2-ethylhexyl)-1 ,4-benzenedicarboxylate; 2-ethylhexyl methyl-1 ,4-benzenedicarboxylate; 1 ,2 cyclohexanedicarboxylic acid, dinonyl ester, branched and linear; bis(2-propylheptyl) phthalate; diisononyl adipate; and a combination thereof.
[0160] The organic plasticizer may have an average, per molecule, of at least one group
of formula
Figure imgf000053_0001
, where R8 represents a hydrogen atom or a monovalent organic group. Alternatively, R8 may represent a branched or linear monovalent hydrocarbon group. The monovalent organic group may be a branched or linear monovalent hydrocarbon group such as an alkyl group of 4 to 15 carbon atoms, alternatively 9 to 12 carbon atoms. Suitable plasticizers may be selected from the group consisting of adipates, carboxylates, phthalates, and a combination thereof.
[0161 ] Alternatively, the organic plasticizer may have an average, per molecule, of at least two groups of the formula above bonded to carbon atoms in a cyclic hydrocarbon. T have general formula:
Figure imgf000053_0002
In this formula, group Z represents a cyclic hydrocarbon group having 3 or more carbon atoms, alternatively 3 to 15 carbon atoms. Subscript k may have a value ranging from 1 to
12. Group Z may be saturated or aromatic. Each R1 0 is independently a hydrogen atom or a branched or linear monovalent organic group. The monovalent organic group for R9 may be an alkyl group such as Me, Et, or Bu. Alternatively, the monovalent organic group for R1 0 may be an ester functional group. Each R9 is independently a branched or linear monovalent hydrocarbon group, such as an alkyl group of 4 to 15 carbon atoms.
[0162] Suitable organic plasticizers are known in the art and are commercially available. The plasticizer may comprise a phthalate, such as: a dialkyl phthalate such as dibutyl phthalate (Eastman™ DBP Plasticizer), diheptyl phthalate, di(2-ethylhexyl) phthalate, or diisodecyl phthalate (DIDP), bis(2-propylheptyl) phthalate (BASF Palatinol® DPHP) , di(2- ethylhexyl) phthalate (Eastman™ DOP Plasticizer), dimethyl phthalate (Eastman™ DMP Plasticizer); diethyl phthalate (Eastman™ DMP Plasticizer); butyl benzyl phthalate, and bis(2-ethylhexyl) terephthalate (Eastman™ 425 Plasticizer); a dicarboxylate such as Benzyl, C7-C9 linear and branched alkyl esters, 1 , 2, benzene dicarboxylic acid (Ferro SANTICIZER® 261 A), 1 ,2,4-benzenetricarboxylic acid (BASF Palatinol® TOTM-I), bis(2- ethylhexyl)-1 ,4-benzenedicarboxylate (Eastman™ 168 Plasticizer); 2-ethylhexyl methyl- 1 ,4-benzenedicarboxylate; 1 ,2 cyclohexanedicarboxylic acid, dinonyl ester, branched and linear (BASF Hexamoll *DINCH); diisononyl adipate; trimellitates such as trioctyl trimellitate (Eastman™ TOTM Plasticizer); triethylene glycol bis(2-ethylhexanoate)
(Eastman™ TEG-EH Plasticizer); triacetin (Eastman™ Triacetin); nonaromatic dibasic acid esters such as dioctyl adipate, bis(2-ethylhexyl) adipate (Eastman™ DOA Plasticizer and Eastman™ DOA Plasticizer, Kosher), di-2-ethylhexyladipate (BASF Plastomoll® DOA), dioctyl sebacate, dibutyl sebacate and diisodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl recinolate; phosphates such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; process oils; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate; tris(2-ethylhexyl) ester; a fatty acid ester; and a combination thereof. Examples of other suitable plasticizers and their commercial sources include BASF Palamoll® 652 and Eastman 168 Xtreme™ Plasticizer.
[0163] Alternatively, a polymer plasticizer can be used. Examples of the polymer plasticizer include alkenyl polymers obtained by polymerizing vinyl or allyl monomers by means of various methods; polyalkylene glycol esters such as diethylene glycol dibenzoate, triethylene glycol dibenzoate and pentaerythritol ester; polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; polyethers including polyether polyols each having a molecular weight of not less than 500 such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polystyrenes such as polystyrene and poly-alpha- methylstyrene; and polybutadiene, polybutene, polyisobutylene, butadiene acrylonitrile, and polychloroprene.
[0164] The polyorganosiloxane extenders and organic plasticizers described above for ingredient (E) may be used either each alone or in combinations of two or more thereof. A low molecular weight organic plasticizer and a higher molecular weight polymer plasticizer may be used in combination. The exact amount of ingredient (E) used in the composition will depend on various factors including the desired end use of the composition and the cured product thereof. However, the amount of ingredient (E) may range from 0.1 % to 10 % based on the combined weights of all ingredients in the composition.
[0165] Ingredient (F) is a filler. The filler may comprise a reinforcing filler, an extending filler, a conductive filler, or a combination thereof. For example, the composition may optionally further comprise ingredient (f 1 ), a reinforcing filler, which when present may be added in an amount ranging from 0.1 % to 95 %, alternatively 1 % to 60 %, based on the weight of the composition. The exact amount of ingredient (f 1 ) depends on various factors including the form of the reaction product of the composition {e.g., gel or rubber) and whether any other fillers are added. Examples of suitable reinforcing fillers include chopped fiber such as chopped KEVLAR®, and/or reinforcing silica fillers such as fume silica, silica aerogel, silica xerogel, and precipitated silica. Fumed silicas are known in the art and commercially available; e.g., fumed silica sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts, U.S.A.
[0166] The composition may optionally further comprise ingredient (f2) an extending filler in an amount ranging from 0.1 % to 95 %, alternatively 1 % to 60 %, and alternatively 1 % to 20 %, based on the weight of the composition. Examples of extending fillers include crushed quartz, aluminum oxide, magnesium oxide, calcium carbonate such as
precipitated calcium carbonate, zinc oxide, talc, diatomaceous earth, iron oxide, clays, mica, titanium dioxide, zirconia, sand, carbon black, graphite, or a combination thereof. Extending fillers are known in the art and commercially available; such as a ground silica sold under the name MIN-U-SIL by U.S. Silica of Berkeley Springs, WV. Suitable precipitated calcium carbonates included Winnofil® SPM from Solvay and Ultrapflex® and Ultrapf lex® 100 from SMI.
[0167] The composition may optionally further comprise ingredient (f3) a conductive filler. Ingredient (F) may be both thermally conductive and electrically conductive. Alternatively, ingredient (F) may be thermally conductive and electrically insulating. Ingredient (F) may be selected from the group consisting of aluminum nitride, aluminum oxide, aluminum trihydrate, barium titanate, beryllium oxide, boron nitride, carbon fibers, diamond, graphite, magnesium hydroxide, magnesium oxide, metal particulate, onyx, silicon carbide, tungsten carbide, zinc oxide, and a combination thereof. Ingredient (F) may comprise a metallic filler, an inorganic filler, a meltable filler, or a combination thereof. Metallic fillers include particles of metals and particles of metals having layers on the surfaces of the particles. These layers may be, for example, metal nitride layers or metal oxide layers on the surfaces of the particles. Suitable metallic fillers are exemplified by particles of metals selected from the group consisting of aluminum, copper, gold, nickel, silver, and combinations thereof, and alternatively aluminum. Suitable metallic fillers are further exemplified by particles of the metals listed above having layers on their surfaces selected from the group consisting of aluminum nitride, aluminum oxide, copper oxide, nickel oxide, silver oxide, and combinations thereof. For example, the metallic filler may comprise aluminum particles having aluminum oxide layers on their surfaces.
[0168] Inorganic conductive fillers are exemplified by onyx; aluminum trihydrate, metal oxides such as aluminum oxide, beryllium oxide, magnesium oxide, and zinc oxide; nitrides such as aluminum nitride and boron nitride; carbides such as silicon carbide and tungsten carbide; and combinations thereof. Alternatively, inorganic conductive fillers are exemplified by aluminum oxide, zinc oxide, and combinations thereof. Meltable fillers may comprise Bi, Ga, In, Sn, or an alloy thereof. The meltable filler may optionally further comprise Ag, Au, Cd, Cu, Pb, Sb, Zn, or a combination thereof. Examples of suitable meltable fillers include Ga, In-Bi-Sn alloys, Sn-ln-Zn alloys, Sn-ln-Ag alloys, Sn-Ag-Bi alloys, Sn-Bi-Cu-Ag alloys, Sn-Ag-Cu-Sb alloys, Sn-Ag-Cu alloys, Sn-Ag alloys, Sn-Ag-Cu- Zn alloys, and combinations thereof. The meltable filler may have a melting point ranging from 50 2C to 250 2C, alternative^ 50 2C to 225 2C. The meltable filler may be a eutectic alloy, a non-eutectic alloy, or a pure metal. Meltable fillers are commercially available.
[0169] For example, meltable fillers may be obtained from Indium Corporation of America, Utica, N.Y. , U.S.A.; Arconium , Providence, R.I., U.S.A.; and AIM Solder, Cranston, R.I., U.S.A. Aluminum fillers are commercially available, for example, from Toyal America, Inc. of Naperville, Illinois, U.S.A. and Valimet Inc., of Stockton, California, U.S.A. Silver filler is commercially available from Metalor Technologies U.S.A. Corp. of Attleboro, Massachusetts, U.S.A.
[0170] Thermally conductive fillers are known in the art and commercially available. For example, CB-A20S and AI-43-Me are aluminum oxide fillers of differing particle sizes commercially available from Showa-Denko, and AA-04, AA-2, and AA18 are aluminum oxide fillers commercially available from Sumitomo Chemical Company. Zinc oxides, such as zinc oxides having trademarks KADOX® and XX®, are commercially available from Zinc Corporation of America of Monaca, Pennsylvania, U.S.A.
[0171 ] The shape of the filler particles is not specifically restricted, however, rounded or spherical particles may prevent viscosity increase to an undesirable level upon high loading of the filler in the composition.
[0172] Ingredient (F) may be a single filler or a combination of two or more fillers that differ in at least one property such as particle shape, average particle size, particle size distribution, and type of filler. For example, it may be desirable to use a combination of fillers, such as a first filler having a larger average particle size and a second filler having a smaller average particle size. Use of a first filler having a larger average particle size and a second filler having a smaller average particle size than the first filler may improve packing efficiency and/or may reduce viscosity of the composition as compared to a composition without such a combination of fillers.
[0173] The average particle size of the filler will depend on various factors including the type of the filler selected for ingredient (F) and the exact amount added to the composition, as well as the end use for the reaction product of the composition. However, the filler may have an average particle size ranging from 0.1 to 80 μιη, alternatively 0.1 to 50 μιη, and alternatively 0.1 to 10 μιη.
[0174] The amount of ingredient (F) in the composition depends on various factors including the end use selected for the composition and the reaction product of the composition, the type and amount of ingredient (B), and the type and amount of the filler selected for ingredient (F). However, the amount of ingredient (F) may range from 0 vol % to 80 vol %, alternatively 50 vol % to 75 vol %, and alternatively 30 % to 80 %, by volume of the composition. Without wishing to be bound by theory, it is thought that when the amount of filler is greater than 80 vol %, the composition may react to form a reaction product with insufficient dimensional integrity for some applications.
[0175] The composition may optionally further comprise ingredient (G) a treating agent. The amount of ingredient (G) will vary depending on factors such as the type of treating agent selected and the type and amount of particulates (such as ingredients (F) and/or (D)) to be treated, and whether the particulates are treated before being added to the composition, or whether the particulates are treated in situ. However, ingredient (G) may be used in an amount ranging from 0.01 % to 20 %, alternatively 0.1 % to 15 %, and alternatively 0.5 % to 5 %, based on the weight of all ingredients in the composition.
Particulates, such as the filler, the physical drying agent, certain flame retardants, and/or certain pigments, when present, may optionally be surface treated with ingredient (G). Particulates may be treated with ingredient (G) before being added to the composition, or in situ. Ingredient (G) may comprise an alkoxysilane, an alkoxy-functional oligosiloxane, a cyclic polyorganosiloxane, a hydroxyl-functional oligosiloxane such as a dimethyl siloxane or methyl phenyl siloxane, or a fatty acid. Examples of fatty acids include stearates such as calcium stearate.
[0176] Some representative organosilicon filler treating agents that can be used as ingredient (G) include compositions normally used to treat silica fillers such as
organochlorosilanes, organosiloxanes, organodisilazanes such as hexaalkyl disilazane, and organoalkoxysilanes such as C6H-| 3Si(OCH3)3, C8H-| 7Si(OC2H5)3,
d 0H21 Si(OCH3)3, d 2H25Si(OCH3)3, d ^gSKCX^Hs^, and C6H5CH2CH2Si(OCH3)3. Other treating agents that can be used include alkylthiols, fatty acids, titanates, titanate coupling agents, zirconate coupling agents, and combinations thereof.
[0177] Alternatively, ingredient (G) may comprise an alkoxysilane having the formula: R1 1 mSi(OR1 2)(4-m) , where subscript m may have a value ranging from 1 to 3, alternatively subscript m is 3. Each R1 1 is independently a monovalent organic group, such as a monovalent hydrocarbon group of 1 to 50 carbon atoms, alternatively 8 to 30 carbon atoms, alternatively 8 to 18 carbon atoms. R1 1 is exemplified by alkyl groups such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; and aromatic groups such as benzyl and phenylethyl. R1 1 may be saturated or unsaturated, and branched or unbranched. Alternatively, R1 1 may be saturated and unbranched.
[0178] Each R1 2 is independently a saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. Alkoxysilanes suitable for use as ingredient (G) are exemplified by hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, phenylethyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and combinations thereof.
[0179] Alkoxy-functional oligosiloxanes may also be used as treating agents. For example, suitable alkoxy-functional oligosiloxanes include those of the formula (V) :
(R1 30)nSi(OSiR1 42R1 5)(4-n). In this formula, subscript n is 1 , 2 or 3, alternatively subscript n is 3. Each R1 3 may be an alkyl group. Each R1 4 may be an unsaturated monovalent hydrocarbon group of 1 to 10 carbon atoms. Each R1 5 may be an unsaturated monovalent hydrocarbon group having at least 10 carbon atoms.
[0180] Certain particulates, such as metal fillers may be treated with alkylthiols such as octadecyl mercaptan; fatty acids such as oleic acid and stearic acid; and a combination thereof.
[0181 ] Treatment agents for alumina or passivated aluminum nitride may include alkoxysilyl functional alkylmethyl polysiloxanes {e.g., partial hydrolysis condensate of
R1 6 0R1 7pSi(OR1 8)(4-o-p) or cohydrolysis condensates or mixtures), or similar materials where the hydrolyzable group may comprise silazane, acyloxy or oximo. In all of these, a group tethered to Si, such as R1 6 in the formula above, is a long chain unsaturated monovalent hydrocarbon or monovalent aromatic-functional hydrocarbon. Each R1 7 is independently a monovalent hydrocarbon group, and each R1 8 is independently a monovalent hydrocarbon group of 1 to 4 carbon atoms. In the formula above, subscript o is 1 , 2, or 3 and subscript p is 0, 1 , or 2, with the proviso that a sum (o + p) is 1 , 2, or 3.
[0182] Other treating agents include alkenyl functional polyorganosiloxanes. Suitable alkenyl functional polyorganosiloxanes include, but are not limited to:
CH3 CH3 CH3
CH2=CH-Si-(OSi)q-OSi-CH3
CH3 CH3 CH3,
where subscript q has a value up to 1 ,500. Other treating agents include mono-endcapped alkoxy functional polydiorganosiloxanes, i.e., polydiorganosiloxanes having an alkoxy group at one end. Such treating agents are exemplified by the formula:
R25R262siO(R262siO)uSi(OR27)3j where subscript u has a value of 0 to 100, alternatively 1 to 50, alternatively 1 to 10, and alternatively 3 to 6. Each R25 is independently selected from an alkyl group, such as Me, Et, Pr, Bu, hexyl, and octyl; and an alkenyl group, such as Vi, allyl, butenyl, and Hex. Each R26 is independently an alkyl group such as Me, Et, Pr, Bu, hexyl, and octyl. Each R27 is independently an alkyl group such as Me, Et, Pr, and Bu. Alternatively, each R25, each R26, and each R27 is Me. Alternatively, each R2^ is Vi. Alternatively, each R2^ and each R27 is Me.
[0183] Alternative, a polyorganosiloxane capable of hydrogen bonding is useful as a treating agent. This strategy to treating surface of a filler takes advantage of multiple hydrogen bonds, either clustered or dispersed or both, as the means to tether the compatibilization moiety to the filler surface. The polyorganosiloxane capable of hydrogen bonding has an average, per molecule, of at least one silicon-bonded group capable of hydrogen bonding. The group may be selected from : an organic group having multiple hydroxyl functionalities or an organic group having at least one amino functional group. The polyorganosiloxane capable of hydrogen bonding means that hydrogen bonding is the primary mode of attachment for the polyorganosiloxane to a filler. The polyorganosiloxane may be incapable of forming covalent bonds with the filler. The polyorganosiloxane capable of hydrogen bonding may be selected from the group consisting of a saccharide- siloxane polymer, an amino-functional polyorganosiloxane, and a combination thereof. Alternatively, the polyorganosiloxane capable of hydrogen bonding may be a saccharide- siloxane polymer. [0184] Ingredient (H) is a biocide. The amount of ingredient (H) will vary depending on factors including the type of biocide selected and the benefit desired. However, the amount of ingredient (H) may range from greater than 0 % to 5 % based on the weight of all ingredients in the composition. Ingredient (H) is exemplified by (hi ) a fungicide, (h2) an herbicide, (h3) a pesticide, (h4) an antimicrobial agent, or a combination thereof.
[0185] Ingredient (hi ) is a fungicide, for example, these include N-substituted benzimidazole carbamate, benzimidazolyl carbamate such as methyl 2- benzimidazolylcarbamate, ethyl 2-benzimidazolylcarbamate, isopropyl 2- benzimidazolylcarbamate, methyl N-{2-[1 -(N,N- dimethylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{2-[1 -(N,N-dimethylcarbamoyl)-6- methylbenzimidazolyl]}carbamate, methyl N-{2-[1 -(N,N-dimethylcarbamoyl)-5- methylbenzimidazolyl]}carbamate, methyl N-{2-[1 -(N-methylcarbamoyl)benzimidazolyl] Jcarbamate, methyl N-{2-[1 -(N-methylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, methyl N-{2-[1 -(N-methylcarbamoyl)-5-methylbenzimidazolyl]}carbamate, ethyl N-{2-[1 - (N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, ethyl N-{2-[2-(N- methylcarbamoyl)benzimidazolyl]}carbamate, ethyl N-{2-[1 -(N,N-dimethylcarbamoyl)-6- methylbenzimidazolyl]}carbamate, ethyl N-{2-[1 -(N-methylcarbamoyl)-6- methylbenzimidazolyl]}carbamate, isopropyl N-{2-[1 -(N,N- dimethylcarbamoyl)benzimidazolyl]}carbamate, isopropyl N-{2-[1 -(N- methylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{2-[1 -(N- propylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{2-[1 -(N- butylcarbamoyl)benzimidazolyl]}carbamate, methoxyethyl N-{2-[1 -(N- propylcarbamoyl)benzimidazolyl]}carbamate, methoxyethyl N-{2-[1 -(N- butylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethyl N-{2-[1 -(N- propylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethyl N-{2-[1 -(N- butylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{1 -(N,N- dimethylcarbamoyloxy)benzimidazolyl]}carbamate, methyl N-{2-[N- methylcarbamoyloxy)benzimidazolyl]}carbamate, methyl N-{2-[1 -(N- butylcarbamoyloxy)benzoimidazolyl]}carbamate, ethoxyethyl N-{2-[1 -(N- propylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethyl N-{2-[1 -(N- butylcarbamoyloxy)benzoimidazolyl]}carbamate, methyl N-{2 -[1 -(N,N-dimethylcarbamoyl)- 6-chlorobenzimidazolyl]}carbamate, and methyl N-{2-[1 -(N,N-dimethylcarbamoyl)-6- nitrobenzimidazolyl]}carbamate; 10, 10'-oxybisphenoxarsine (which has trade name Vinyzene, OBPA), di-iodomethyl-para-tolylsulfone, benzothiophene-2- cyclohexylcarboxamide-S,S-dioxide, N-(fluordichloridemethylthio)phthalimide (which has trade names Fluor-Folper, and Preventol A3); methyl-benzimideazol-2-ylcarbamate (which has trade names Carbendazim, and Preventol BCM), zinc-bis(2-pyridylthio-1 -oxide) (zinc pyrithion) 2-(4-thiazolyl)-benzimidazol, N-phenyl-iodpropargylcarbamate, N-octyl-4- isothiazolin-3-on, 4,5-dichloride-2-n-octyl-4-isothiazolin-3-on, N-butyl-1 ,2-benzisothiazolin- 3-on and/or triazolyl-compounds, such as tebuconazol in combination with zeolites containing silver.
[0186] Ingredient (h2) is an herbicide, for example, suitable herbicides include amide herbicides such as allidochlor /V,/V-diallyl-2-chloroacetamide; CDEA 2-chloro-/V,/V- diethylacetamide; etnipromid (RS)-2-[5-(2,4-dichlorophenoxy)-2-nitrophenoxy]-/V- ethylpropionamide; anilide herbicides such as cisanilide c/'s-2,5-dimethylpyrrolidine-1 - carboxanilide; flufenacet 4'-fluoro-/V-isopropyl-2-[5-(trifluoromethyl)-1 ,3,4-thiadiazol-2- yloxy]acetanilide; naproanilide (RS)-a-2-naphthoxypropionanilide; arylalanine herbicides such as benzoylprop N-benzoyl-/V-(3,4-dichlorophenyl)-DL-alanine; flamprop-M /V-benzoyl- /V-(3-chloro-4-fluorophenyl)-D-alanine; chloroacetanilide herbicides such as butachlor N- butoxymethyl-2-chloro-2',6'-diethylacetanilide; metazachlor 2-chloro-/V-(pyrazol-1 - ylmethyl)acet-2',6'-xylidide; prynachlor (RS)-2-chloro-/V-(1 -methylprop-2-ynyl)acetanilide; sulphonanilide herbicides such as cloransulam 3-chloro-2-(5-ethoxy-7- fluoro[1 ,2,4]triazolo[1 ,5-c]pyrimidin-2-ylsulphonamido)benzoic acid; metosulam 2',6'- dichloro-5,7-dimethoxy-3'-methyl[1 ,2,4]triazolo[1 ,5-a]pyrimidine-2-sulphonanilide; antibiotic herbicides such as bilanafos 4-[hydroxy(methyl)phosphinoyl]-L-homoalanyl-L-alanyl-L- alanine; benzoic acid herbicides such as chloramben 3-amino-2,5-dichlorobenzoic acid; 2,3,6-TBA 2,3,6-trichlorobenzoic acid; pyrimidinyloxybenzoic acid herbicides such as bispyribac 2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid; pyrimidinylthiobenzoic acid herbicides such as pyrithiobac 2-chloro-6-(4,6-dimethoxypyrimidin-2-ylthio)benzoic acid; phthalic acid herbicides such as chlorthal tetrachloroterephthalic acid; picolinic acid herbicides such as aminopyralid 4-amino-3,6-dichloropyridine-2-carboxylic acid;
quinolinecarboxylic acid herbicides such as quinclorac 3,7-dichloroquinoline-8-carboxylic acid; arsenical herbicides such as CMA calcium bis(hydrogen methylarsonate); MAMA ammonium hydrogen methylarsonate; sodium arsenite; benzoylcyclohexanedione herbicides such as mesotrione 2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1 ,3-dione;
benzofuranyl alkylsulphonate herbicides such as benfuresate 2,3-dihydro-3,3- dimethylbenzofuran-5-yl ethanesulphonate; carbamate herbicides such as carboxazole methyl 5-ferf-butyl-1 ,2-oxazol-3-ylcarbamate; fenasulam methyl 4-[2-(4-chloro-o- tolyloxy)acetamido]phenylsulphonylcarbamate; carbanilate herbicides such as BCPC {RS)- sec-butyl 3-chlorocarbanilate; desmedipham ethyl 3-phenylcarbamoyloxyphenylcarbamate; swep methyl 3,4-dichlorocarbanilate; cyclohexene oxime herbicides such as butroxydim (RS)-(EZ)-5-(3-butyryl-2,4,6-trimethylphenyl)-2-(1 -ethoxyiminopropyl)-3-hydroxycyclohex-2- en-1 -one; tepraloxydim (RS)-(EZ)-2-{\ -[(2E)-3-chloroallyloxyimino]propyl}-3-hydroxy-5- perhydropyran-4-ylcyclohex-2-en-1 -one; cyclopropylisoxazole herbicides such as isoxachlortole 4-chloro-2-mesylphenyl 5-cyclopropyl-1 ,2-oxazol-4-yl ketone; dicarboximide herbicides such as flumezin 2-methyl-4-(a,a,a-trifluoro-m-tolyl)-1 ,2,4-oxadiazinane-3,5- dione; dinitroaniline herbicides such as ethalfluralin N-ethyl-a,a,a-trifluoro-N-(2-methylallyl)- 2,6-dinitro-p-toluidine; prodiamine 5-dipropylamino-a,a,a-trifluoro-4,6-dinitro-o-toluidine; dinitrophenol herbicides such as dinoprop 4,6-dinitro-o-cymen-3-ol; etinofen oethoxy-4,6- dinitro-o-cresol; diphenyl ether herbicides such as ethoxyfen 0-[2-chloro-5-(2-chloro-a,a,a- trifluoro-p-tolyloxy)benzoyl]-L-lactic acid; nitrophenyl ether herbicides such as aclonifen 2- chloro-6-nitro-3-phenoxyaniline; nitrofen 2,4-dichlorophenyl 4-nitrophenyl ether;
dithiocarbamate herbicides such as dazomet 3,5-dimethyl-1 ,3,5-thiadiazinane-2-thione; halogenated aliphatic herbicides such as dalapon 2,2-dichloropropionic acid; chloroacetic acid; imidazolinone herbicides such as imazapyr (RS)-2-(4-isopropyl-4-methyl-5-oxo-2- imidazolin-2-yl)nicotinic acid; inorganic herbicides such as disodium tetraborate decahydrate; sodium azide; nitrile herbicides such as chloroxynil 3,5-dichloro-4- hydroxybenzonitrile; ioxynil 4-hydroxy-3,5-di-iodobenzonitrile; organophosphorus herbicides such as anilofos S-4-chloro-N-isopropylcarbaniloylmethyl 0,0-dimethyl phosphorodithioate; glufosinate 4-[hydroxy(methyl)phosphinoyl]-DL-homoalanine; phenoxy herbicides such as clomeprop (RS)-2-(2,4-dichloro-m-tolyloxy)propionanilide; fenteracol 2- (2,4,5-trichlorophenoxy)ethanol; phenoxyacetic herbicides such as MCPA (4-chloro-2- methylphenoxy)acetic acid; phenoxybutyric herbicides such as MCPB 4-(4-chloro-o- tolyloxy)butyric acid; phenoxypropionic herbicides such as fenoprop (RS)-2-(2,4,5- trichlorophenoxy)propionic acid; aryloxyphenoxypropionic herbicides such as isoxapyrifop (RS)-2-[2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionyl]isoxazolidine; phenylenediamine herbicides such as dinitramine Λ/1 ,/V1 -diethyl-2,6-dinitro-4-trifluoromethyl-m- phenylenediamine, pyrazolyloxyacetophenone herbicides such as pyrazoxyfen 2-[4-(2,4- dichlorobenzoyl)-1 ,3-dimethylpyrazol-5-yloxy]acetophenone; pyrazolylphenyl herbicides such as pyraflufen 2-chloro-5-(4-chloro-5-difluoromethoxy-1 -methylpyrazol-3-yl)-4- fluorophenoxyacetic acid; pyridazine herbicides such as pyridafol 6-chloro-3- phenylpyridazin-4-ol; pyridazinone herbicides such as chloridazon 5-amino-4-chloro-2- phenylpyridazin-3(2/-/)-one; oxapyrazon 5-bromo-1 ,6-dihydro-6-oxo-1 -phenylpyridazin-4- yloxamic acid; pyridine herbicides such as fluroxypyr 4-amino-3,5-dichloro-6-fluoro-2- pyridyloxyacetic acid; thiazopyr methyl 2-difluoromethyl-5-(4,5-dihydro-1 ,3-thiazol-2-yl)-4- isobutyl-6-trifluoromethylnicotinate; pyrimidinediamine herbicides such as iprymidam 6- chloro-N^isopropylpyrimidine^^-diamine; quaternary ammonium herbicides such as diethamquat 1 J '^is(diethylcarbamoylmethyl)-4,4'-bipyridinium; paraquat 1 ,1 '-dimethyl-4,4'- bipyridinium; thiocarbamate herbicides such as cycloate S-ethyl
cyclohexyl(ethyl)thiocarbamate; tiocarbazil S-benzyl di-sec-butylthiocarbamate;
thiocarbonate herbicides such as EXD 0,0-diethyl dithiobis(thioformate); thiourea herbicides such as methiuron 1 ,1 -dimethyl-3-m-tolyl-2-thiourea; triazine herbicides such as triaziflam (f?S)-/V-[2-(3,5-dimethylphenoxy)-1 -methylethyl]-6-(1 -fluoro-1 -methylethyl)-1 ,3,5- triazine-2,4-diamine; chlorotriazine herbicides such as cyprazine 6-chloro-/V2-cyclopropyl-
Λ/4-isopropyl-l ,3,5-triazine-2,4-diamine; propazine e-chloro-N^/N^-di-isopropyl-l ,3,5- triazine-2,4-diamine; methoxytriazine herbicides such as prometon /V2,/v4-di-isopropyl-6- methoxy-1 ,3,5-triazine-2,4-diamine; methylthiotriazine herbicides such as cyanatryn 2-(4- ethylamino-6-methylthio-1 ,3,5-triazin-2-ylamino)-2-methylpropionitrile; triazinone herbicides such as hexazinone 3-cyclohexyl-6-dimethylamino-1 -methyl-1 ,3,5-triazine-2,4(1 H,3H)- dione; triazole herbicides such as epronaz /V-ethyl-/V-propyl-3-propylsulphonyl-1 H-1 ,2,4- triazole-1 -carboxamide; triazolone herbicides such as carfentrazone (RS)-2-chloro-3-{2- chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1 H-1 ,2,4-triazol-1 -yl]-4- fluorophenyljpropionic acid; triazolopyrimidine herbicides such as florasulam 2',6',8- trifluoro-5-methoxy[1 ,2,4]triazolo[1 ,5-c]pyrimidine-2-sulphonanilide; uracil herbicides such as flupropacil isopropyl 2-chloro-5-(1 ,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4- trifluoromethylpyrimidin-1 -yl)benzoate; urea herbicides such as cycluron 3-cyclo-octyl-1 ,1 - dimethylurea; monisouron 1 -(5-ferf-butyl-1 ,2-oxazol-3-yl)-3-methylurea; phenylurea herbicides such as chloroxuron 3-[4-(4-chlorophenoxy)phenyl]-1 ,1 -dimethylurea; siduron 1 - (2-methylcyclohexyl)-3-phenylurea; pyrimidinylsulphonylurea herbicides such as flazasulphuron 1 -(4,6-dimethoxypyrimidin-2-yl)-3-(3-trifluoromethyl-2-pyridylsulphonyl)urea; pyrazosulphuron 5-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulphamoyl]-1 -methylpyrazole- 4-carboxylic acid; triazinylsulphonylurea herbicides such as thifensulphuron 3-(4-methoxy- 6-methyl-1 ,3,5-triazin-2-ylcarbamoylsulphamoyl)thiophene-2-carboxylic acid;
thiadiazolylurea herbicides such as tebuthiuron 1 -(5-feri-butyl-1 ,3,4-thiadiazol-2-yl)-1 ,3- dimethylurea; and/or unclassified herbicides such as chlorfenac (2,3,6- trichlorophenyl)acetic acid; methazole 2-(3,4-dichlorophenyl)-4-methyl-1 ,2,4- oxadiazolidine-3,5-dione; tritac (RS)-1 -(2,3,6-trichlorobenzyloxy)propan-2-ol; 2,4-D, chlorimuron, and fenoxaprop; and combinations thereof.
[0187] Ingredient (h3) is a pesticide. Suitable pesticides are exemplified by atrazine, diazinon, and chlorpyrifos. For purposes of this application, pesticide includes insect repellents such as Ν,Ν-diethyl-meta-toluamide and pyrethroids such as pyrethrin. [0188] Ingredient (h4) is an antimicrobial agent. Suitable antimicrobials are commercially available, such as DOW CORNING® 5700 and DOW CORNING® 5772, which are from Dow Corning Corporation of Midland, Michigan, U.S.A.
[0189] Alternatively, ingredient (H) may comprise a boron containing material, e.g., boric anhydride, borax, or disodium octaborate tetrahydrate; which may function as a pesticide, fungicide, and/or flame retardant.
[0190] Ingredient (I) is a stabilizer that may be used for altering the reaction rate of the composition, as compared to a composition containing the same ingredients but with the stabilizer omitted. Stabilizers for hydrosilylation curable compositions are exemplified by acetylenic alcohols such as methyl butynol, ethynyl cyclohexanol, dimethyl hexynol, and 3,5-dimethyl-1 -hexyn-3-ol, 1 -butyn-3-ol, 1 -propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1 - butyn-3-ol, 3-methyl-1 -pentyn-3-ol, 3-phenyl-1 -butyn-3-ol, 4-ethyl-1 -octyn-3-ol, 3,5- diemthyl-1 -hexyn-3-ol, and 1 -ethynyl-1 -cyclohexanol, and a combination thereof;
cycloalkenylsiloxanes such as methylvinylcyclosiloxanes exemplified by 1 ,3,5,7- tetramethyl-1 ,3,5,7-tetravinylcyclotetrasiloxane, 1 ,3,5,7-tetramethyM ,3,5,7- tetrahexenylcyclotetrasiloxane, and a combination thereof; ene-yne compounds such as 3- methyl-3-penten-1 -yne, 3,5-dimethyl-3-hexen-1 -yne; triazoles such as benzotriazole;
phosphines; mercaptans; hydrazines; amines, such as tetramethyl ethylenediamine, dialkyi fumarates, dialkenyl fumarates, dialkoxyalkyl fumarates, maleates such as diallyl maleate; nitriles; ethers; carbon monoxide; alkenes such as cyclo-octadiene,
divinyltetramethyldisiloxane; alcohols such as benzyl alcohol; and a combination thereof.
[0191] Alternatively, ingredient (I) in the composition may be a silylated acetylenic compound. Without wishing to be bound by theory, it is thought that adding a silylated acetylenic compound reduces yellowing of the reaction product prepared from
hydrosilylation reaction of the composition as compared to a reaction product from hydrosilylation of a composition that does not contain a silylated acetylenic compound or that contains an organic acetylenic alcohol stabilizer, such as those described above.
[0192] The silylated acetylenic compound is exemplified by (3-methyl-1 -butyn-3- oxy)trimethylsilane, ((1 ,1 -dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1 -butyn-3- oxy)dimethylsilane, bis(3-methyl-1 -butyn-3-oxy)silanemethylvinylsilane, bis((1 ,1 -dimethyl-2- propynyl)oxy)dimethylsilane, methyl(tris(1 ,1 -dimethyl-2-propynyloxy))silane, methyl(tris(3- methyl-1 -butyn-3-oxy))silane, (3-methyl-1 -butyn-3-oxy)dimethylphenylsilane, (3-methyl-1 - butyn-3-oxy)dimethylhexenylsilane, (3-methyl-1 -butyn-3-oxy)triethylsilane, bis(3-methyl-1 - butyn-3-oxy)methyltrifluoropropylsilane, (3,5-dimethyl-1 -hexyn-3-oxy)trimethylsilane, (3- phenyl-1 -butyn-3-oxy)diphenylmethylsilane, (3-phenyl-1 -butyn-3-oxy)dimethylphenylsilane, (3-phenyl-1 -butyn-3-oxy)dimethylvinylsilane, (3-phenyl-1 -butyn-3- oxy)dimethylhexenylsilane, (cyclohexyl-1 -ethyn-1 -oxy)dimethylhexenylsilane, (cyclohexyl- 1 -ethyn-1 -oxy)dimethylvinylsilane, (cyclohexyl-1 -ethyn-1 -oxy)diphenylmethylsilane, (cyclohexyl-1 -ethyn-1 -oxy)trimethylsilane, and combinations thereof. Alternatively, ingredient (I) is exemplified by methyl(tris(1 ,1 -dimethyl-2-propynyloxy))silane, ((1 ,1 - dimethyl-2-propynyl)oxy)trimethylsilane, or a combination thereof. The silylated acetylenic compound useful as ingredient (I) may be prepared by methods known in the art, such as silylating an acetylenic alcohol described above by reacting it with a chlorosilane in the presence of an acid receptor.
[0193] The amount of stabilizer added to the composition will depend on various factors including the desired pot life of the composition, whether the composition will be a one part composition or a multiple part composition, the particular stabilizer used, and the selection and amount of ingredient (C), if present. However, when present, the amount of stabilizer may range from 0 % to 1 %, alternatively 0% to 5%, alternatively 0.001 % to 1 %, alternatively 0.01 % to 0.5 %, and alternatively 0.0025 % to 0.025 %, based on the weight of all ingredients in the composition.
[0194] Ingredient (J) is a flame retardant. Suitable flame retardants may include, for example, carbon black, hydrated aluminum hydroxide, and silicates such as wollastonite, platinum and platinum compounds. Alternatively, the flame retardant may be selected from halogen based flame-retardants such as decabromodiphenyloxide, octabromodiphenyl oxide, hexabromocyclododecane, decabromobiphenyl oxide, diphenyoxybenzene, ethylene bis- tetrabromophthalmide, pentabromoethyl benzene, pentabromobenzyl acrylate, tribromophenyl maleic imide, tetrabromobisphenyl A, bis-(tribromophenoxy) ethane, bis- (pentabromophenoxy) ethane, polydibomophenylene oxide, tribromophenylallyl ether, bis- dibromopropyl ether, tetrabromophthalic anhydride, dibromoneopentyl gycol, dibromoethyl dibromocyclohexane, pentabromodiphenyl oxide, tribromostyrene,
pentabromochlorocyclohexane, tetrabromoxylene, hexabromocyclododecane, brominated polystyrene, tetradecabromodiphenoxybenzene, trifluoropropene and PVC. Alternatively, the flame retardant may be selected from phosphorus based flame-retardants such as (2,3- dibromopropyl)-phosphate, phosphorus, cyclic phosphates, triaryl phosphate, bis- melaminium pentate, pentaerythritol bicyclic phosphate, dimethyl methyl phosphate, phosphine oxide diol, triphenyl phosphate, tris- (2-chloroethyl) phosphate, phosphate esters such as tricreyl, trixylenyl, isodecyl diphenyl, ethylhexyl diphenyl, phosphate salts of various amines such as ammonium phosphate, trioctyl, tributyl or tris-butoxyethyl phosphate ester. Other flame retardants may include tetraalkyl lead compounds such as tetraethyl lead, iron pentacarbonyl, manganese methyl cyclopentadienyl tricarbonyl, melamine and derivatives such as melamine salts, guanidine, dicyandiamide, ammonium sulphamate, alumina trihydrate, and magnesium hydroxide alumina trihydrate.
[0195] The amount of flame retardant will vary depending on factors such as the flame retardant selected and whether solvent is present. However, the amount of flame retardant in the composition may range from greater than 0 % to 10 % based on the weight of all ingredients in the composition.
[0196] Ingredient (K) is a surface modifier. Suitable surface modifiers are exemplified by (k1 ) an adhesion promoter and (k2) a release agent. Suitable adhesion promoters for ingredient (k1 ) may comprise a transition metal chelate, a hydrocarbonoxysilane such as an alkoxysilane, a combination of an alkoxysilane and a hydroxy-functional
polyorganosiloxane, an aminofunctional silane, or a combination thereof. Adhesion promoters are known in the art and may comprise silanes having the formula
R19RR20 sSi(OR21 )4_(r + S) where each R1 9 is independently a monovalent organic group having at least 3 carbon atoms; R20 contains at least one SiC bonded substituent having an adhesion-promoting group, such as amino, epoxy, mercapto or acrylate groups;
subscript r has a value ranging from 0 to 2; subscript s is either 1 or 2; and the sum of (r + s) is not greater than 3. Alternatively, the adhesion promoter may comprise a partial condensate of the above silane. Alternatively, the adhesion promoter may comprise a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane.
[0197] Alternatively, the adhesion promoter may comprise an unsaturated or epoxy- functional compound. The adhesion promoter may comprise an unsaturated or epoxy- functional alkoxysilane. For example, the functional alkoxysilane can have the formula
R22tSi(OR23)(4-t), where subscript t is 1 , 2, or 3, alternatively subscript t is 1 . Each R22 is independently a monovalent organic group with the proviso that at least one R22 is an unsaturated organic group or an epoxy-functional organic group. Epoxy-functional organic groups for R22 are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl.
Unsaturated organic groups for R22 are exemplified by 3-methacryloyloxypropyl, 3- acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecylenyl. Each R23 is independently a saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. R23 is exemplified by Me, Et, Pr, and Bu.
[0198] Examples of suitable epoxy-functional alkoxysilanes include 3- glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,
(epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane and combinations thereof. Examples of suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3- methacryloyloxypropyl triethoxysilane, 3-acryloyloxypropyl trimethoxysilane, 3- acryloyloxypropyl triethoxysilane, and combinations thereof.
[0199] Alternatively, the adhesion promoter may comprise an epoxy-functional siloxane such as a reaction product of a hydroxy-terminated polyorganosiloxane with an epoxy- functional alkoxysilane, as described above, or a physical blend of the hydroxy-terminated polyorganosiloxane with the epoxy-functional alkoxysilane. The adhesion promoter may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane. For example, the adhesion promoter is exemplified by a mixture of 3- glycidoxypropyltrimethoxysilane and a reaction product of hydroxy-terminated
methylvinylsiloxane with 3-glycidoxypropyltrimethoxysilane, or a mixture of 3- glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated
methylvinyl/dimethylsiloxane copolymer.
[0200] Alternatively, the adhesion promoter may comprise an aminofunctional silane, such as an aminofunctional alkoxysilane exemplified by H2N(CH2)2Si(OCH3)3,
H2N(CH2)2Si(OCH2CH3)3, H2N(CH2)3Si(OCH3)3, H2N(CH2)3Si(OCH2CH3)3, CH3NH(CH2)3Si(OCH3)3, CH3NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)5Si(OCH3)3, CH3NH(CH2)5Si(OCH2CH3)3, H2N(CH2)2NH(CH2)3Si(OCH3)3,
H2N(CH2)2NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH3)3,
CH3NH(CH2)2NH(CH2)3Si(OCH2CH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH2CH3)3, H2N(CH2)2SiCH3(OCH3)2,
H2N(CH2)2SiCH3(OCH2CH3)2, H2N(CH2)3SiCH3(OCH3)2,
H2N(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)3SiCH3(OCH3)2,
CH3NH(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)5SiCH3(OCH3)2,
CH3NH(CH2)5SiCH3(OCH2CH3)2, H2N(CH2)2NH(CH2)3SiCH3(OCH3)2,
H2N(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, and a combination thereof.
[0201 ] Alternatively, the adhesion promoter may comprise a transition metal chelate. Suitable transition metal chelates include titanates, zirconates such as zirconium acetylacetonate, aluminum chelates such as aluminum acetylacetonate, and combinations thereof. Alternatively, the adhesion promoter may comprise a combination of a transition metal chelate with an alkoxysilane, such as a combination of
glycidoxypropyltrimethoxysilane with an aluminum chelate or a zirconium chelate.
[0202] Ingredient (k2) is a release agent. Suitable release agents are exemplified by fluorinated compounds, such as fluoro-functional silicones, or fluoro-functional organic compounds.
[0203] Alternatively, the surface modifier for ingredient (K) may be used to change the appearance of the surface of a reaction product of the composition. For example, surface modifier may be used to increase gloss of the surface of a reaction product of the composition. Such a surface modifier may comprise a polydiorganosiloxane with alkyl and aryl groups. For example, DOW CORNING® 550 Fluid is a trimethylsiloxy-terminated poly(dimethyl/methylphenyl)siloxane with a viscosity of 125 cSt that is commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.
[0204] Alternatively, ingredient (K) may be a natural oil obtained from a plant or animal source, such as linseed oil, tung oil, soybean oil, castor oil, fish oil, hempseed oil, cottonseed oil, oiticica oil, or rapeseed oil.
[0205] The exact amount of ingredient (K) depends on various factors including the type of surface modifier selected as ingredient (K) and the end use of the composition and its reaction product. However, ingredient (K), when present, may be added to the composition in an amount ranging from 0.01 to 50 weight parts based on the weight of the composition, alternatively 0.01 to 10 weight parts, and alternatively 0.01 to 5 weight parts. Ingredient (K) may be one adhesion promoter. Alternatively, ingredient (K) may comprise two or more different surface modifiers that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence.
[0206] Chain lengtheners may include difunctional silanes and difunctional siloxanes, which extend the length of polyorganosiloxane chains before crosslinking occurs. Chain lengtheners may be used to reduce the modulus of elongation of the cured product. Chain lengtheners compete in their reactions with aliphatically unsaturated groups and/or silicon bonded hydrogen atoms in other ingredients of the composition, e.g., ingredients (B) and/or ingredient (C), when present. Dimethylhydrogensiloxy-terminated polydimethylsiloxanes having relatively low degrees of polymerization {e.g., DP ranging from 3 to 50) may be used as ingredient (L). Ingredient (L) may be one chain lengthener Alternatively, ingredient (L) may comprise two or more different chain lengtheners that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence [0207] Ingredient (M) is and endblocker comprising an M-unit, i.e., a siloxane unit of formula R243SiO-|/2, where each R24 independently represents a monovalent, nonfunctional, organic group, such as a monovalent hydrocarbon group free of aliphatic unsaturation. Ingredient (M) may comprise polyorganosiloxanes endblocked on one terminal end by a triorganosilyl group, e.g., (CH3)3SiO-, and on the other end by a silicon bonded hydrogen atom and/or an aliphatically unsaturated organic group. Ingredient (M) may be a polydiorganosiloxane such as a polydimethylsiloxane. The
polydiorganosiloxanes having both silicon bonded hydrogen terminals and triorganosilyl end groups, may have more than 50 %, alternatively more than 75 %, of the total end groups as silicon bonded hydrogen atoms. The amount of triorganosilyl group in the polydimethylsiloxane may be used to regulate the modulus of a cured product prepared by curing the composition. Without wishing to be bound by theory, it is thought that higher concentrations of triorganosilyl end groups may provide a lower modulus in cured products. Ingredient (M) may be one endblocker. Alternatively, ingredient (M) may comprise two or more different endblockers that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence.
[0208] Ingredient (N) is a flux agent. The composition may comprise 0 % to 2 % of the flux agent based on the weight of all ingredients in the composition. Molecules containing chemically active functional groups such as carboxylic acid and amines can be used as flux agents. Such flux agents can include aliphatic acids such as succinic acid, abietic acid, oleic acid, and adipic acid; aromatic acids such as benzoic acids; aliphatic amines and their derivatives, such as triethanolamine, hydrochloride salts of amines, and hydrobromide salts of amines. Flux agents are known in the art and are commercially available.
[0209] Ingredient (O) is an anti-aging additive. The anti-aging additive may comprise an antioxidant, a UV absorber, a UV stabilizer, a heat stabilizer, or a combination thereof. Suitable antioxidants are known in the art and are commercially available. Suitable antioxidants include phenolic antioxidants and combinations of phenolic antioxidants with stabilizers. Phenolic antioxidants include fully sterically hindered phenols and partially hindered phenols; and sterically hindered amines such as tetramethyl-piperidine derivatives. Suitable phenolic antioxidants include vitamin E and IRGANOX® 1010 from Ciba Specialty Chemicals, U.S.A. IRGANOX® 1010 comprises pentaerythritol tetrakis(3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate). Examples of UV absorbers include phenol, 2- (2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-, branched and linear (TINUVIN® 571 ).
Examples of UV stabilizers include bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) sebacate; methyl 1 ,2,2,6,6-pentamethyl-4-piperidyl/sebacate; and a combination thereof (TINUVIN® 272). These and other TINUVIN® additives, such as TINUVIN® 765 are commercially available from Ciba Specialty Chemicals of Tarrytown, NY, U.S.A. Other UV and light stabilizers are commercially available, and are exemplified by LowLite from Chemtura, OnCap from PolyOne, and Light Stabilizer 210 from E. I. du Pont de Nemours and Company of Delaware, U.S.A. Oligomeric (higher molecular weight) stabilizers may alternatively be used, for example, to minimize potential for migration of the stabilizer out of the composition or the cured product thereof. An example of an oligomeric antioxidant stabilizer (specifically, hindered amine light stabilizer (HALS)) is Ciba TINUVIN® 622, which is a dimethylester of butanedioic acid copolymerized with 4-hydroxy-2,2,6,6- tetramethyl-1 -piperidine ethanol. Heat stabilizers may include iron oxides and carbon blacks, iron carboxylate salts, cerium hydrate, barium zirconate, cerium and zirconium octoates, and porphyrins.
[0210] The amount of ingredient (O) depends on various factors including the specific anti-aging additive selected and the anti-aging benefit desired. However, the amount of ingredient (O) may range from 0 to 5 weight %, alternatively 0.1 % to 4 %, and alternatively 0.5 to 3 weight %, based on the weight of all ingredients in the composition. Ingredient (O) may be one anti-aging additive. Alternatively, ingredient (O) may comprise two or more different anti-aging additives.
[0211 ] Ingredient (P) is a pigment. For purposes of this application, the term 'pigment' includes any ingredient used to impart color to a reaction product of a composition described herein. The amount of pigment depends on various factors including the type of pigment selected and the desired degree of coloration of the product. For example, the composition may comprise 0 to 20 %, alternatively 0.001 % to 5 %, of a pigment based on the weight of all ingredients in the composition.
[0212] Examples of suitable pigments include indigo, titanium dioxide Stan-Tone 50SP01 Green (which is commercially available from PolyOne) and carbon black. Representative, non-limiting examples of carbon black include Shawinigan Acetylene black, which is commercially available from Chevron Phillips Chemical Company LP; SUPERJET® Carbon Black (LB-101 1 ) supplied by Elementis Pigments Inc., of Fairview Heights, IL U.S.A.; SR 51 1 supplied by Sid Richardson Carbon Co, of Akron, OH U.S.A.; and N330, N550, N762, N990 (from Degussa Engineered Carbons of Parsippany, NJ, U.S.A.).
[0213] Ingredient (Q) is an acid acceptor. Suitable acid acceptors include magnesium oxide, calcium oxide, and combinations thereof. The composition may comprise 0 % to 2 % of ingredient (Q) based on the weight of the composition.
[0214] The composition may optionally further comprise up to 5 %, alternatively 1 % to 2 % based on the weight of the composition of ingredient (R) a rheological additive for modifying rheology of the composition. Rheological additives are known in the art and are commercially available. Examples include polyamides, Polyvest, which is commercially available from Evonk, Disparlon from King Industries, Kevlar Fibre Pulp from Du Pont, Rheospan from Nanocor, and Ircogel from Lubrizol. Other suitable rheological additives include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate and barium stearate, and combinations thereof.
[0215] Alternatively, ingredient (R) may comprise a microcrystalline wax that is a solid at 25 °C (wax). The melting point may be selected such that the wax has a melting point at the low end of the desired application temperature range. Without wishing to be bound by theory, it is thought that ingredient (R) acts as a process aid that improves flow properties of the composition. Without wishing to be bound by theory, it is thought that incorporation of wax may also facilitate incorporation of fillers, compounding and de-airing (during production of the composition), and mixing (static or dynamic mixing during application of parts of a multiple part composition). It is thought that the wax, when molten, serves as a process aid, substantially easing the incorporation of filler in the composition during compounding, the compounding process itself, as well as in during a de-airing step, if used. The wax, with a melt temperature below 100 °C, may facilitate mixing of the parts of a multiple part composition before application, even in a simple static mixer.
[0216] Waxes suitable for use as ingredient (R) may be non-polar hydrocarbons. The waxes may have branched structures, cyclic structures, or combinations thereof. For example, petroleum microcrystalline waxes are available from Strahl & Pitsch, Inc., of West Babylon, NY, U.S.A. and include SP 96 (melting point ranging from 62 2C to 69 2C), SP 18 (melting point ranging from 73 2C to 80 2C), SP 19 (melting point ranging from 76 2C to 83 2C), SP 26 (melting point ranging from 76 2C to 83 2C), SP 60 (melting point ranging from 79 2C to 85 2C), SP 617 (melting point ranging from 88 2C to 93 2C), SP 89 (melting point ranging from 90 2C to 95 2C), and SP 624 (melting point ranging from 90 2C to 95 2C). Other petroleum microcrystalline waxes include waxes marketed under the trademark Multiwax® by Crompton Corporation of Petrolia, Pennsylvania, U.S.A. These waxes include 180-W, which comprises saturated branched and cyclic non-polar hydrocarbons and has melting point ranging from 79 2C to 87 2C; Multiwax® W-445, which comprises saturated branched and cyclic non-polar hydrocarbons, and has melting point ranging from 76 °C to 83 2C; and Multiwax® W-835, which comprises saturated branched and cyclic non-polar hydrocarbons, and has melting point ranging from 73 2C to 80 2C.
[0217] The amount of ingredient (R) depends on various factors including the specific rheological additive selected and the selections of the other ingredients of the composition. However, the amount of ingredient (R) may range from 0 parts to 20 parts, alternatively 1 parts to 15 parts, and alternatively 1 part to 5 parts based on the weight of all ingredients in the composition. Ingredient (R) may be one rheological additive. Alternatively, ingredient (R) may comprise two or more different rheological additives.
[0218] A vehicle may be used in the composition. The vehicle may facilitate flow of the composition and introduction of certain ingredients, such as silicone resin. Vehciles used herein are those that help fluidize the ingredients of the composition but essentially do not react with the ingredients. The vehicle may be selected based on solubility the ingredients in the composition and volatility. The solubility refers to the vehicle being sufficient to dissolve and/or disperse ingredients of the composition. Volatility refers to vapor pressure of the vehicle. If the vehicle is too volatile (having too high vapor pressure) bubbles may form in the composition during hydrosilylation reaction, and the bubbles may cause cracks or otherwise weaken or detrimentally affect properties of the reaction product. However, if the vehicle is not volatile enough (too low vapor pressure) the vehicle may remain as a plasticizer in the reaction product of the composition.
[0219] Suitable vehicles include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane and other low molecular weight polyorganosiloxanes, such as 0.5 to 1 .5 cSt Dow Corning® 200 Fluids and Dow Corning® OS FLUIDS, which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.
[0220] Alternatively, the vehicle may comprise an organic solvent. The organic solvent can be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n- butyl ether, a halogenated hydrocarbon such as dichloromethane, 1 ,1 ,1 -trichloroethane or methylene chloride; chloroform; dimethyl sulfoxide; dimethyl formamide, acetonitrile;
tetrahydrofuran; white spirits; mineral spirits; naphtha; n-methyl pyrrolidone; or a combination thereof.
[0221 ] The amount of vehicle will depend on various factors including the type of vehicle selected and the amount and type of other ingredients selected for the composition.
However, the amount of vehicle may range from 1 % to 99%, alternatively 2 % to 50 %, based on the weight of all ingredients in the composition. Ingredient (S) can be added during preparation of the composition, for example, to aid mixing and delivery. All or a portion of ingredient (S) may optionally be removed after the composition is prepared. [0222] Ingredient (T) is a surfactant. Suitable surfactants include silicone polyethers, ethylene oxide polymers, propylene oxide polymers, copolymers of ethylene oxide and propylene oxide, other non-ionic surfactants, and combinations thereof. The composition may comprise 0 % to 0.05 % of the surfactant based on the weight of all ingredients in the composition.
[0223] Ingredient (U) is a corrosion inhibitor. Examples of suitable corrosion inhibitors include benzotriazole, mercaptabenzotriazole and commercially available corrosion inhibitors such as 2,5-dimercapto-1 ,3,4-thiadiazole derivative (CUVAN® 826) and alkylthiadiazole (CUVAN® 484) from R. T. Vanderbilt of Norwalk, Connecticut, U.S.A. When present, the amount of ingredient (U) may range from 0.05 % to 0.5 % based on the weight of the composition.
[0224] When selecting ingredients for the composition described above, there may be overlap between types of ingredients because certain ingredients described herein may have more than one function. For example, certain alkoxysilanes may be useful as filler treating agents and as adhesion promoters, and certain plasticizers such as fatty acid esters may also be useful as filler treating agents. Certain particulates may be useful as fillers and as pigments, and even as flame retardants, e.g., carbon black. When adding additional ingredients to the composition, the additional ingredients are distinct from one another.
[0225] The composition can be prepared by a method comprising combining all ingredients by any convenient means such as mixing at ambient or elevated temperature. Ingredient (I), when present, may be added before ingredient (A), for example, when the composition will be prepared at elevated temperature and/or the composition will be prepared as a one part composition.
[0226] When ingredient (G) is present, the composition may optionally be prepared by surface treating a particulate ingredient {e.g., filler and/or spacer, if present) with ingredient (G), and thereafter mixing the product thereof with the other ingredients of the composition.
[0227] Alternatively, the composition may be prepared as a multiple part composition, for example, when ingredient (I) is absent, or when the composition will be stored for a long period of time before use. In the multiple part composition, ingredient (A) is stored in a separate part from any ingredient having a silicon bonded hydrogen atom, for example ingredient (C), and the parts are combined shortly before use of the composition. For example, a two part composition may be prepared by combining ingredients comprising (B), (A), (F), and optionally one or more other additional ingredients described above to form a base by any convenient means such as mixing. A curing agent may be prepared by combining ingredients comprising (B), (C), and optionally one or more other additional ingredients described above by any convenient means such as mixing. The ingredients may be combined at ambient or elevated temperature. When a two part composition is used, the weight ratio of amounts of base to curing agent may range from 1 :1 to 10:1 . The composition will react via hydrosilylation reaction to form a reaction product. The reaction product may have various forms, such as a silane, a gum, a gel, a rubber, or a resin.
EXAMPLES
[0228] These examples are intended to illustrate some embodiments of the invention and should not be interpreted as limiting the scope of the invention set forth in the claims. The following ingredients were used in the examples.
[0229] The aliphatically unsaturated compound can be styrene (B1 ), 1 -octene (B2), or 1 - hexene (B3), all of which are also available from Sigma-Aldrich. Or, the aliphatically unsaturated compound can be (B4) a vinyl terminated polydimethylsiloxane, containing 2.6 meq silicon bonded vinyl groups and having Mw of 9400 and viscosity of 200 cSt, which is commercially available as DMS-V22 from Gelest, Inc. of Morrisville, Pennsylvania, U.S.A. The SiH functional compound can be (C1 ) a trimethylsiloxy-terminated,
poly(methylhydrogen)siloxane ("MDHM") having Mw ranging from 1 ,800 to 2,100 and SiH content of 2.6 meq, which is commercially available as HMS-992, also from Gelest, Inc. Alternatively, the SiH functional compound can be (C2) Phenylsilane ('Ή βίΡΙΥ'), which is commercially available from Sigma-Aldrich.
[0230] The control catalyst was DOW CORNING® 2-0707 INT, which is a complex of Pt with a polyorganosiloxane. DOW CORNING® 2-0707 INT is commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.
[0231] One or more of the following model reactions may be used to test catalytic activity of a reaction product prepared as described above for ingredient (A). Ingredients (B3) and (C2) were used in the [PhSi] reaction to attempt to make a reaction product [I] comprising PhSiHz(C6H-| 3)(3-z). Ingredients (B3) and (C1 ) were used in the [HMTS] reaction to attempt to make a reaction product [II] comprising (H3C)3Si-0-Si(CH2)(C6H-| 3)-0-
Si(CH3)3.
(A) M-Ligand
Complex
[PhSi] Rxn Product [I]
Figure imgf000075_0001
CH3 CH3 CH3 H (A) M-Ligand
I I I . /CH„ Complex
[HMTS] H3C-Si-0-Si-0-Si-CH3 + H2C- ^C P_ ^ Rxn Product [II]
CH3 H CH3
Reference Example - Formation of Metal Precursor
[0232] Anhydrous N1I2 purchased from Strem Chemicals, 0.273 gm (0.87 mmol), was dissolved in 14.8 gm THF and was cooled at -35 °C. Lithium bis(trimethylsilyl)amide (1 M in THF) purchased from Aldrich, 1 .64 gm (1 .84 mmol), was mixed with 14.8 gm THF and added slowly into the N1I2 solution at -35 °C under agitation. The solution turned from green/brown to dark brown after the addition of Lithium bis(trimethylsilyl)amide solution. The temperature was raised to room temperature and heated to 60 °C for 3 hours under agitation. The resulting solution at 0.025 M was used as precursor Ni-2 in the examples below.
Example 1- Formation of Metal-Ligand complexes
[0233] Precursor solutions were prepared by mixing a Ni precursor at a 0.025 molar (M) concentration with THF or, if the precursor was insoluble in THF, then a suitable solvent to dissolve the ligand selected from dimethylsulfoxide (DMSO), toluene, and hexane. Nickel (II) bromide dimethoxyethane, and Nickel (II) bis trimethylsilyl amide were used as the Ni precursors. Solutions of each ligand shown above in Table 2 were also prepared by mixing the ligand at a 0.025 M concentration with THF. Each ligand solution prepared above was dispensed into 2 milliliter (mL) vials at 85 microliters (μί) per vial. To prepare samples to evaluate as ingredient (A), one of the metal precursor solutions described above was added to a vial containing a ligand, and an additional 85 microliters (μί) THF was added, and the vial contents were mixed at 300 RPM at room temperature of 25 °C for 2 hours. A sufficient amount of metal precursor solution was added such that the Metal : Ligand Ratio was either 1 : 1 or 1 : 2. The resulting mixture in the vial was cooled to a temperature of - 17 °C. An activator was added, and the vial was allowed to return to room temperature. The activator was 95 μL· at 0.05 M concentration of either LiBArF in THF or NaEt3BH in toluene. The vial contents were mixed for 2 hours. The resulting vial contents were evaluated for use in catalyzing hydrosilylation.
Example 2 - [PhSi] Reaction [0234] To perform the [PhSi] reaction, PhSiH3 (C2) in dodecane and 1 -hexene (B3) were added to a vial prepared according to Example 1 . The amount of PhSiH3 (C2) added to the vial was either 170 μΙ_ of 6.25 M (as H or SiH) PhSiH3 (C2) in dodecane, or 132.4μΙ_
PhSiH3 (C2) in 37.6 μL· dodecane. The amount of 1 -hexene (B3) was 145 μΙ_. Each vial was mixed overnight (for 16 h) at 50 °C. The resulting contents of each vial were analyzed by GC according to the method described below.
Example 3 - [HMTS] Reaction
[0235] To perform the [HMTS] reaction, 1 -hexene (B3) and 1 ,1 ,1 ,3,5,5,5- heptamethyltrisiloxane (C1 ) were added to a vial prepared according to Example 1 . The amount of 1 -hexene added was 145 μΙ_. The amount of heptamethyltrisiloxane (C1 ) was either 312 μΙ_ heptamethyltrisiloxane (C1 ) at a concentration of 3.4 M (as H or SiH) in dodecane, or 290 μΙ_ heptamethyltrisiloxane (C1 ) in 22 μΙ_ dodecane. Each vial was mixed overnight (for 16 h) at 50 °C. The resulting contents of each vial were analyzed by GC according to the method described below.
Example 4 - GC Measurement
[0236] A gas chromatography (GC) analysis was made of the samples prepared in an example above. The GC analysis was performed with a Hewlett-Packard 7890A gas chromatograph with a flame ionization detector (FID). A Leap Combi-Pal robot was used to perform the injections in an automated manner. The system was configured as detailed in Table 3.
Table 3: GC-FID Experimental Parameter Settings.
Carrier gas - 99.9998% high purity helium
Detector - FID at 280 °C, H2 = 30 mL/min, Air = 300 mL/min, Make up He = 45 mL/min
GC inlet, split - 275 °C, split ratio = 200:1 , constant pressure (total flow 22.5 mL/min) GC column - Agilent Low Thermal Mass column, 350 °C, 30m X 320μιη X 0.25μιη
GC temperature program - 55(3) to 300(5) @35 °C/min, 15 minute total run time
Internal standard - 5% (w/w) dodecane in phenylsilane
data system - Agilent Technologies ChemStation
[0237] The GC temperature program details are as follows in Table 4 with the oven at a constant temperautre of 300 °C.
Table 4
LTM column 1 LTM column 2 Rate Value *Hold Run Rate Value *Hold Run ( °C/min) ( °C) Time time ( O/min) ( °C) Time time
(min) (min) (min) (min)
100 0.5 0.5 100 2 2
50 150 0.5 2 50 150 0.5 3.5
600 300 5 7 600 300 3.5 7
*Difference to allow for delay oefore second injection
[0238] Dodecane was used as an internal standard to gravimetrically quantify the chromatographic analyses. Internal standard was introduced prior to reaction at 5% (w/w) from a solution of dodecane and phenylsilane. Theoretical response factors for the analytes were calculated and entered into the ChemStation to automatically create a calibration table and quantitatively calculate the concentration of an analyte in the presence of an internal standard (Equation 1 ).
RFanalyte = ([analyte]/Areaana|yte) x (Area|S/[IS]) x RF!S (1 )
[0239] The terms in Equation 1 are defined as follows: RFana|yte = response factor for the analyte, [analyte] = concentration of the analyte, Areaana|yte = peak area of the analyte, Areais = peak area of the internal standard, [IS] = concentration of the internal standard, RF|s = response factor for the internal standard.
[0240] Encompassing experimental and instrumental errors, the relative standard deviation of the measurements ranged from 0.3% to 1 0% depending on the concentration and, correspondingly, the yield of the analyte. The results are in Table 5.
Table 5 - Results
Figure imgf000077_0001
Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-1 488 HMTS LiBArF 4.25 1:2 No
Ni-1 488 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 510 HMTS NaEt3BH 2.125 1:1 No
Ni-1 510 HMTS NaEt3BH 4.25 1:2 Yes
Ni-1 510 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 512 HMTS LiBArF 4.25 1:2 No
Ni-1 512 P SiH3 LiBArF 4.25 1:2 No
Ni-1 604 HMTS LiBArF 2.125 1:1 No
Ni-1 604 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 635 HMTS LiBArF 2.125 1:1 No
Ni-1 635 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 732 HMTS LiBArF 2.125 1:1 No
Ni-1 734 HMTS LiBArF 2.125 1:1 No
Ni-1 734 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 735 HMTS NaEt3BH 2.125 1:1 No
Ni-1 735 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 748 HMTS NaEt3BH 4.25 1:2 No
Ni-1 748 P SiH3 NaEt3BH 4.25 1:2 No
Ni-1 755 HMTS NaEt3BH 2.125 1:1 No
Ni-1 755 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 777 HMTS LiBArF 4.25 1:2 No
Ni-1 777 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 785 HMTS LiBArF 2.125 1:1 No
Ni-1 785 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 788 HMTS NaEt3BH 2.125 1:1 No
Ni-1 788 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 799 HMTS NaEt3BH 2.125 1:1 No
Ni-1 799 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 805 HMTS NaEt3BH 2.125 1:1 No Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-1 819 HMTS LiBArF 2.125 1:1 No
Ni-1 819 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 1116 HMTS NaEt3BH 2.125 1:1 No
Ni-1 1116 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 1125 HMTS LiBArF 4.25 1:2 No
Ni-1 1125 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 1214 HMTS LiBArF 2.125 1:1 No
Ni-1 1214 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 1249 HMTS NaEt3BH 2.125 1:1 No
Ni-1 1249 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 1430 HMTS LiBArF 2.125 1:1 No
Ni-1 1430 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 1483 HMTS NaEt3BH 4.25 1:2 No
Ni-1 1483 P SiH3 NaEt3BH 4.25 1:2 No
Ni-1 1547 HMTS NaEt3BH 2.125 1:1 No
Ni-1 1547 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 1769 HMTS LiBArF 4.25 1:2 No
Ni-1 1769 P SiH3 LiBArF 4.25 1:2 No
Ni-1 1832 HMTS LiBArF 4.25 1:2 No
Ni-1 1832 P SiH3 LiBArF 4.25 1:2 No
Ni-1 1888 HMTS LiBArF 4.25 1:2 No
Ni-1 1888 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 1936 HMTS NaEt3BH 4.25 1:2 No
Ni-1 1936 HMTS NaEt3BH 4.25 1:2 Yes
Ni-1 1936 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 2061 HMTS LiBArF 4.25 1:2 No
Ni-1 2061 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 2062 HMTS LiBArF 2.125 1:1 No
Ni-1 2062 P SiH3 LiBArF 2.125 1:1 Yes Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-1 2072 HMTS LiBArF 2.125 1:1 No
Ni-1 2072 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 2075 HMTS NaEt3BH 4.25 1:2 No
Ni-1 2075 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 2272 HMTS NaEt3BH 2.125 1:1 No
Ni-1 2272 HMTS NaEt3BH 2.125 1:1 Yes
Ni-1 2272 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 2363 HMTS LiBArF 4.25 1:2 No
Ni-1 2363 P SiH3 LiBArF 4.25 1:2 No
Ni-1 2806 HMTS NaEt3BH 4.25 1:2 No
Ni-1 2806 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 2816 HMTS LiBArF 4.25 1:2 No
Ni-1 2816 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 2915 HMTS NaEt3BH 2.125 1:1 No
Ni-1 2915 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 2920 HMTS LiBArF 2.125 1:1 No
Ni-1 2920 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 2921 HMTS LiBArF 2.125 1:1 No
Ni-1 2921 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 2927 HMTS NaEt3BH 2.125 1:1 No
Ni-1 2956 HMTS LiBArF 4.25 1:2 No
Ni-1 2956 HMTS NaEt3BH 4.25 1:2 No
Ni-1 2956 HMTS NaEt3BH 4.25 1:2 Yes
Ni-1 2956 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 2956 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 3096 HMTS LiBArF 2.125 1:1 No
Ni-1 3096 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 3179 HMTS NaEt3BH 4.25 1:2 No
Ni-1 3179 P SiH3 NaEt3BH 4.25 1:2 Yes Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-1 3191 HMTS NaEt3BH 2.125 1:1 No
Ni-1 3191 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 3472 HMTS NaEt3BH 2.125 1:1 No
Ni-1 3472 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 3499 HMTS LiBArF 2.125 1:1 No
Ni-1 3499 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 3500 HMTS NaEt3BH 2.125 1:1 No
Ni-1 3500 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 3505 HMTS LiBArF 2.125 1:1 No
Ni-1 3505 P SiH3 LiBArF 2.125 1:1 No
Ni-1 3544 HMTS NaEt3BH 4.25 1:2 No
Ni-1 3544 P SiH3 NaEt3BH 4.25 1:2 No
Ni-1 3547 HMTS LiBArF 2.125 1:1 No
Ni-1 3547 P SiH3 LiBArF 2.125 1:1 No
Ni-1 3586 HMTS LiBArF 4.25 1:2 No
Ni-1 3586 P SiH3 LiBArF 4.25 1:2 No
Ni-1 3746 HMTS NaEt3BH 2.125 1:1 No
Ni-1 3746 HMTS NaEt3BH 2.125 1:1 Yes
Ni-1 3746 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 3749 HMTS LiBArF 2.125 1:1 No
Ni-1 3749 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 4098 HMTS NaEt3BH 4.25 1:2 No
Ni-1 4098 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 4117 HMTS NaEt3BH 4.25 1:2 No
Ni-1 4117 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 4151 HMTS LiBArF 4.25 1:2 No
Ni-1 4151 P SiH3 LiBArF 4.25 1:2 No
Ni-1 4202 HMTS LiBArF 2.125 1:1 No
Ni-1 4202 P SiH3 LiBArF 2.125 1:1 Yes Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-1 4226 HMTS LiBArF 4.25 1:2 No
Ni-1 4226 P SiH3 LiBArF 4.25 1:2 No
Ni-1 4548 HMTS NaEt3BH 4.25 1:2 No
Ni-1 4548 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 4570 HMTS NaEt3BH 2.125 1:1 No
Ni-1 4570 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 4990 HMTS LiBArF 4.25 1:2 No
Ni-1 4990 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 5177 HMTS NaEt3BH 4.25 1:2 No
Ni-1 5177 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 5479 HMTS LiBArF 2.125 1:1 No
Ni-1 5479 P SiH3 LiBArF 2.125 1:1 No
Ni-1 6253 HMTS LiBArF 4.25 1:2 No
Ni-1 6253 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 6269 HMTS LiBArF 2.125 1:1 No
Ni-1 6269 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 6322 HMTS NaEt3BH 4.25 1:2 No
Ni-1 6322 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 6340 HMTS LiBArF 4.25 1:2 No
Ni-1 6340 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 6372 HMTS NaEt3BH 4.25 1:2 No
Ni-1 6372 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 6417 HMTS NaEt3BH 2.125 1:1 Yes
Ni-1 6510 HMTS LiBArF 4.25 1:2 No
Ni-1 6510 P SiH3 LiBArF 4.25 1:2 No
Ni-1 6870 HMTS NaEt3BH 2.125 1:1 No
Ni-1 6870 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 6886 HMTS NaEt3BH 2.125 1:1 No
Ni-1 7124 HMTS LiBArF 2.125 1:1 No Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-1 7124 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 7282 HMTS NaEt3BH 2.125 1:1 No
Ni-1 7282 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 7377 HMTS LiBArF 2.125 1:1 No
Ni-1 7377 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 7471 HMTS NaEt3BH 4.25 1:2 No
Ni-1 7471 P SiH3 NaEt3BH 4.25 1:2 No
Ni-1 7496 HMTS NaEt3BH 4.25 1:2 No
Ni-1 7496 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 7534 HMTS NaEt3BH 4.25 1:2 No
Ni-1 7534 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 7639 HMTS LiBArF 2.125 1:1 No
Ni-1 7639 P SiH3 LiBArF 2.125 1:1 No
Ni-1 8500 HMTS LiBArF 4.25 1:2 No
Ni-1 8500 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 8538 HMTS NaEt3BH 4.25 1:2 No
Ni-1 8538 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 8749 HMTS LiBArF 4.25 1:2 No
Ni-1 8749 P SiH3 LiBArF 4.25 1:2 No
Ni-1 8768 HMTS LiBArF 2.125 1:1 No
Ni-1 8768 P SiH3 LiBArF 2.125 1:1 No
Ni-1 8838 HMTS NaEt3BH 2.125 1:1 No
Ni-1 8838 HMTS NaEt3BH 2.125 1:1 Yes
Ni-1 8842 HMTS LiBArF 2.125 1:1 No
Ni-1 8842 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 8856 HMTS NaEt3BH 2.125 1:1 No
Ni-1 8856 HMTS NaEt3BH 2.125 1:1 Yes
Ni-1 8856 P SiH3 NaEt3BH 2.125 1:1 No
Ni-1 8881 HMTS NaEt3BH 4.25 1:2 No Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-1 8881 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 8945 HMTS NaEt3BH 2.125 1:1 No
Ni-1 8945 HMTS NaEt3BH 2.125 1:1 Yes
Ni-1 8945 P SiH3 NaEt3BH 2.125 1:1 No
Ni-1 8946 HMTS LiBArF 2.125 1:1 No
Ni-1 8977 HMTS LiBArF 4.25 1:2 No
Ni-1 8977 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 9042 HMTS NaEt3BH 2.125 1:1 No
Ni-1 9042 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 9072 HMTS NaEt3BH 4.25 1:2 No
Ni-1 9072 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10132 HMTS NaEt3BH 2.125 1:1 No
Ni-1 10132 HMTS NaEt3BH 2.125 1:1 Yes
Ni-1 10132 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 10150 HMTS LiBArF 2.125 1:1 No
Ni-1 10218 HMTS NaEt3BH 2.125 1:1 No
Ni-1 10218 HMTS NaEt3BH 2.125 1:1 Yes
Ni-1 10218 P SiH3 NaEt3BH 2.125 1:1 No
Ni-1 10267 HMTS LiBArF 2.125 1:1 No
Ni-1 10364 HMTS NaEt3BH 2.125 1:1 No
Ni-1 10364 HMTS NaEt3BH 2.125 1:1 Yes
Ni-1 10364 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 10374 HMTS LiBArF 4.25 1:2 Yes
Ni-1 10374 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 10376 HMTS NaEt3BH 2.125 1:1 No
Ni-1 10376 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 10377 HMTS LiBArF 4.25 1:2 No
Ni-1 10377 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 10379 HMTS NaEt3BH 4.25 1:2 No Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-1 10379 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10380 HMTS LiBArF 4.25 1:2 No
Ni-1 10380 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 10381 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10381 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10383 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10383 P SiH3 NaEt3BH 4.25 1:2 No
Ni-1 10384 HMTS LiBArF 4.25 1:2 No
Ni-1 10384 P SiH3 LiBArF 4.25 1:2 No
Ni-1 10385 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10385 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10386 HMTS LiBArF 4.25 1:2 No
Ni-1 10386 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 10387 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10387 P SiH3 NaEt3BH 4.25 1:2 No
Ni-1 10389 HMTS NaEt3BH 2.125 1:1 No
Ni-1 10389 P SiH3 NaEt3BH 2.125 1:1 No
Ni-1 10390 HMTS LiBArF 2.125 1:1 No
Ni-1 10390 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 10391 HMTS LiBArF 4.25 1:2 No
Ni-1 10391 P SiH3 LiBArF 4.25 1:2 No
Ni-1 10392 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10392 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10394 HMTS NaEt3BH 2.125 1:1 No
Ni-1 10394 HMTS NaEt3BH 2.125 1:1 Yes
Ni-1 10394 P SiH3 NaEt3BH 2.125 1:1 No
Ni-1 10398 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10398 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10399 HMTS LiBArF 4.25 1:2 No Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-1 10399 P SiH3 LiBArF 4.25 1:2 No
Ni-1 10400 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10400 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10403 HMTS NaEt3BH 2.125 1:1 No
Ni-1 10403 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 10404 HMTS LiBArF 2.125 1:1 No
Ni-1 10404 P SiH3 LiBArF 2.125 1:1 No
Ni-1 10405 HMTS NaEt3BH 2.125 1:1 No
Ni-1 10405 HMTS NaEt3BH 2.125 1:1 Yes
Ni-1 10405 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-1 10406 HMTS LiBArF 2.125 1:1 No
Ni-1 10406 P SiH3 LiBArF 2.125 1:1 No
Ni-1 10407 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10407 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10441 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10441 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10444 HMTS LiBArF 4.25 1:2 No
Ni-1 10444 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 10445 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10445 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10446 HMTS LiBArF 2.125 1:1 No
Ni-1 10446 P SiH3 LiBArF 2.125 1:1 Yes
Ni-1 10447 HMTS NaEt3BH 2.125 1:1 No
Ni-1 10447 P SiH3 NaEt3BH 2.125 1:1 No
Ni-1 10450 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10450 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10451 HMTS LiBArF 4.25 1:2 No
Ni-1 10451 P SiH3 LiBArF 4.25 1:2 No
Ni-1 10452 HMTS NaEt3BH 4.25 1:2 No Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-1 10452 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10453 HMTS LiBArF 4.25 1:2 No
Ni-1 10453 P SiH3 LiBArF 4.25 1:2 Yes
Ni-1 10454 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10454 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-1 10455 HMTS LiBArF 4.25 1:2 No
Ni-1 10455 P SiH3 LiBArF 4.25 1:2 No
Ni-1 10456 HMTS NaEt3BH 4.25 1:2 No
Ni-1 10456 P SiH3 NaEt3BH 4.25 1:2 No
Ni-1 10457 HMTS LiBArF 4.25 1:2 No
Ni-1 10457 P SiH3 LiBArF 4.25 1:2 No
Ni-2 165 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 165 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 483 HMTS NaEt3BH 4.25 1:2 No
Ni-2 483 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 483 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 484 HMTS LiBArF 4.25 1:2 No
Ni-2 484 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 486 HMTS NaEt3BH 4.25 1:2 No
Ni-2 486 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 486 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 488 HMTS NaEt3BH 4.25 1:2 No
Ni-2 488 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 488 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 510 HMTS LiBArF 4.25 1:2 No
Ni-2 510 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 512 HMTS NaEt3BH 4.25 1:2 No
Ni-2 512 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 512 P SiH3 NaEt3BH 4.25 1:2 Yes Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-2 604 HMTS NaEt3BH 2.125 1:1 No
Ni-2 604 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 604 P SiH3 NaEt3BH 2.125 1:1 No
Ni-2 635 HMTS NaEt3BH 2.125 1:1 No
Ni-2 635 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 635 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 732 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 732 P SiH3 NaEt3BH 2.125 1:1 No
Ni-2 734 HMTS NaEt3BH 237.111 1:111.6 No
Ni-2 734 P SiH3 NaEt3BH 237.111 1:111.6 No
Ni-2 735 HMTS LiBArF 2.125 1:1 No
Ni-2 735 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 748 HMTS LiBArF 4.25 1:2 No
Ni-2 748 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 755 HMTS LiBArF 2.125 1:1 No
Ni-2 755 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 777 HMTS NaEt3BH 4.25 1:2 No
Ni-2 777 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 777 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 785 HMTS NaEt3BH 2.125 1:1 No
Ni-2 785 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 785 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 788 HMTS LiBArF 2.125 1:1 No
Ni-2 788 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 799 HMTS LiBArF 2.125 1:1 No
Ni-2 799 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 805 HMTS LiBArF 2.125 1:1 No
Ni-2 805 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 819 HMTS NaEt3BH 2.125 1:1 No Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-2 819 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 819 P SiH3 NaEt3BH 2.125 1:1 No
Ni-2 1116 HMTS LiBArF 2.125 1:1 No
Ni-2 1116 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 1125 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 1125 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 1214 HMTS NaEt3BH 2.125 1:1 No
Ni-2 1214 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 1214 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 1249 HMTS LiBArF 2.125 1:1 No
Ni-2 1249 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 1430 HMTS NaEt3BH 2.125 1:1 No
Ni-2 1430 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 1430 P SiH3 NaEt3BH 2.125 1:1 No
Ni-2 1483 HMTS LiBArF 4.25 1:2 No
Ni-2 1483 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 1547 HMTS LiBArF 2.125 1:1 No
Ni-2 1547 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 1769 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 1769 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 1832 HMTS NaEt3BH 4.25 1:2 No
Ni-2 1832 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 1832 P SiH3 NaEt3BH 4.25 1:2 No
Ni-2 1888 HMTS NaEt3BH 4.25 1:2 No
Ni-2 1888 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 1888 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 1936 HMTS LiBArF 4.25 1:2 No
Ni-2 1936 HMTS LiBArF 4.25 1:2 Yes
Ni-2 1936 P SiH3 LiBArF 4.25 1:2 Yes Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-2 2061 HMTS NaEt3BH 4.25 1:2 No
Ni-2 2061 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 2062 HMTS NaEt3BH 2.125 1:1 No
Ni-2 2062 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 2062 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 2072 HMTS NaEt3BH 2.125 1:1 No
Ni-2 2072 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 2072 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 2075 HMTS LiBArF 4.25 1:2 No
Ni-2 2075 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 2272 HMTS LiBArF 2.125 1:1 No
Ni-2 2272 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 2363 HMTS NaEt3BH 4.25 1:2 No
Ni-2 2363 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 2806 HMTS LiBArF 4.25 1:2 No
Ni-2 2806 HMTS LiBArF 4.25 1:2 Yes
Ni-2 2806 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 2816 HMTS NaEt3BH 4.25 1:2 No
Ni-2 2816 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 2915 HMTS LiBArF 2.125 1:1 No
Ni-2 2915 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 2920 HMTS NaEt3BH 2.125 1:1 No
Ni-2 2920 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 2920 P SiH3 NaEt3BH 2.125 1:1 No
Ni-2 2921 HMTS NaEt3BH 2.125 1:1 No
Ni-2 2921 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 2921 P SiH3 NaEt3BH 2.125 1:1 No
Ni-2 2927 HMTS LiBArF 2.125 1:1 No
Ni-2 2927 P SiH3 LiBArF 2.125 1:1 Yes Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-2 2956 HMTS LiBArF 4.25 1:2 No
Ni-2 2956 HMTS LiBArF 4.25 1:2 Yes
Ni-2 2956 HMTS NaEt3BH 4.25 1:2 No
Ni-2 2956 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 2956 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 2956 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 3096 HMTS NaEt3BH 2.125 1:1 No
Ni-2 3096 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 3096 P SiH3 NaEt3BH 2.125 1:1 No
Ni-2 3179 HMTS LiBArF 4.25 1:2 No
Ni-2 3179 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 3191 HMTS LiBArF 2.125 1:1 No
Ni-2 3191 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 3472 HMTS LiBArF 2.125 1:1 No
Ni-2 3472 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 3499 HMTS NaEt3BH 2.125 1:1 No
Ni-2 3499 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 3499 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 3500 HMTS LiBArF 2.125 1:1 No
Ni-2 3500 HMTS LiBArF 2.125 1:1 Yes
Ni-2 3500 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 3505 HMTS NaEt3BH 2.125 1:1 No
Ni-2 3505 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 3544 HMTS LiBArF 4.25 1:2 No
Ni-2 3544 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 3547 HMTS NaEt3BH 2.125 1:1 No
Ni-2 3547 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 3547 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 3586 HMTS NaEt3BH 4.25 1:2 No Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-2 3586 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 3746 HMTS LiBArF 2.125 1:1 No
Ni-2 3746 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 3749 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 3749 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 4098 HMTS LiBArF 4.25 1:2 No
Ni-2 4098 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 4117 HMTS LiBArF 4.25 1:2 No
Ni-2 4117 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 4151 HMTS NaEt3BH 4.25 1:2 No
Ni-2 4151 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 4202 HMTS NaEt3BH 2.125 1:1 No
Ni-2 4202 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 4202 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 4226 HMTS NaEt3BH 4.25 1:2 No
Ni-2 4226 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 4548 HMTS LiBArF 4.25 1:2 Yes
Ni-2 4548 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 4570 HMTS LiBArF 2.125 1:1 No
Ni-2 4570 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 4990 HMTS NaEt3BH 4.25 1:2 No
Ni-2 4990 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 5177 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 5479 HMTS NaEt3BH 2.125 1:1 No
Ni-2 5479 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 5479 P SiH3 NaEt3BH 2.125 1:1 No
Ni-2 6253 HMTS NaEt3BH 4.25 1:2 No
Ni-2 6253 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 6253 P SiH3 NaEt3BH 4.25 1:2 Yes Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-2 6269 HMTS NaEt3BH 2.125 1:1 No
Ni-2 6269 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 6269 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 6322 HMTS LiBArF 4.25 1:2 No
Ni-2 6322 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 6340 HMTS NaEt3BH 4.25 1:2 No
Ni-2 6340 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 6340 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 6372 HMTS LiBArF 4.25 1:2 No
Ni-2 6372 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 6417 HMTS LiBArF 2.125 1:1 No
Ni-2 6417 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 6510 HMTS NaEt3BH 4.25 1:2 No
Ni-2 6510 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 6870 HMTS LiBArF 2.125 1:1 No
Ni-2 6870 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 6886 HMTS LiBArF 2.125 1:1 No
Ni-2 6886 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 7124 HMTS NaEt3BH 2.125 1:1 No
Ni-2 7124 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 7124 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 7282 HMTS LiBArF 2.125 1:1 No
Ni-2 7282 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 7377 HMTS NaEt3BH 2.125 1:1 No
Ni-2 7377 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 7471 HMTS LiBArF 4.25 1:2 No
Ni-2 7471 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 7496 HMTS LiBArF 2.125 1:1 No
Ni-2 7496 HMTS LiBArF 4.25 1:2 Yes Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-2 7496 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 7534 HMTS LiBArF 4.25 1:2 No
Ni-2 7534 HMTS LiBArF 4.25 1:2 Yes
Ni-2 7534 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 7639 HMTS NaEt3BH 2.125 1:1 No
Ni-2 7639 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 8500 HMTS NaEt3BH 4.25 1:2 No
Ni-2 8500 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 8500 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 8538 HMTS LiBArF 4.25 1:2 No
Ni-2 8538 HMTS LiBArF 4.25 1:2 Yes
Ni-2 8538 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 8749 HMTS NaEt3BH 4.25 1:2 No
Ni-2 8749 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 8749 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 8768 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 8768 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 8838 HMTS LiBArF 2.125 1:1 No
Ni-2 8838 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 8842 HMTS NaEt3BH 2.125 1:1 No
Ni-2 8842 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 8842 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 8856 HMTS LiBArF 2.125 1:1 No
Ni-2 8856 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 8881 HMTS LiBArF 4.25 1:2 No
Ni-2 8881 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 8945 HMTS LiBArF 2.125 1:1 Yes
Ni-2 8945 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 8946 HMTS NaEt3BH 2.125 1:1 Yes Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-2 8946 P SiH3 NaEt3BH 2.125 1:1 No
Ni-2 8977 HMTS NaEt3BH 2.125 1:1 No
Ni-2 8977 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 8977 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 9042 HMTS LiBArF 2.125 1:1 No
Ni-2 9042 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 9072 HMTS LiBArF 4.25 1:2 Yes
Ni-2 9072 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 10132 HMTS LiBArF 2.125 1:1 Yes
Ni-2 10132 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 10150 HMTS NaEt3BH 2.125 1:1 No
Ni-2 10150 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 10150 P SiH3 NaEt3BH 2.125 1:1 No
Ni-2 10218 HMTS LiBArF 2.125 1:1 No
Ni-2 10218 P SiH3 LiBArF 2.125 1:1 No
Ni-2 10267 HMTS NaEt3BH 2.125 1:1 No
Ni-2 10267 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 10267 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 10364 HMTS LiBArF 2.125 1:1 No
Ni-2 10364 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 10374 HMTS NaEt3BH 4.25 1:2 No
Ni-2 10374 P SiH3 NaEt3BH 4.25 1:2 No
Ni-2 10376 HMTS LiBArF 2.125 1:1 No
Ni-2 10376 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 10377 HMTS NaEt3BH 4.25 1:2 No
Ni-2 10377 P SiH3 NaEt3BH 4.25 1:2 No
Ni-2 10379 HMTS LiBArF 4.25 1:2 No
Ni-2 10379 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 10380 HMTS NaEt3BH 4.25 1:2 No Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-2 10380 HMTS NaEt3BH 4.25 1:2 Yes
Ni-2 10380 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 10381 HMTS LiBArF 4.25 1:2 No
Ni-2 10381 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 10383 HMTS LiBArF 4.25 1:2 No
Ni-2 10383 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 10384 HMTS NaEt3BH 4.25 1:2 No
Ni-2 10384 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 10385 HMTS LiBArF 4.25 1:2 No
Ni-2 10385 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 10386 HMTS NaEt3BH 4.25 1:2 No
Ni-2 10386 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 10387 HMTS LiBArF 4.25 1:2 No
Ni-2 10387 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 10389 HMTS LiBArF 2.125 1:1 No
Ni-2 10389 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 10390 HMTS NaEt3BH 2.125 1:1 No
Ni-2 10390 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 10390 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 10391 HMTS NaEt3BH 4.25 1:2 No
Ni-2 10391 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 10392 HMTS LiBArF 4.25 1:2 No
Ni-2 10392 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 10394 HMTS LiBArF 2.125 1:1 No
Ni-2 10394 P SiH3 LiBArF 2.125 1:1 No
Ni-2 10398 HMTS LiBArF 4.25 1:2 No
Ni-2 10398 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 10399 HMTS NaEt3BH 4.25 1:2 No
Ni-2 10399 P SiH3 NaEt3BH 4.25 1:2 Yes Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-2 10400 HMTS LiBArF 4.25 1:2 No
Ni-2 10400 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 10403 HMTS LiBArF 2.125 1:1 No
Ni-2 10403 P SiH3 LiBArF 2.125 1:1 No
Ni-2 10404 HMTS NaEt3BH 2.125 1:1 No
Ni-2 10404 HMTS NaEt3BH 2.125 1:1 Yes
Ni-2 10404 P SiH3 NaEt3BH 2.125 1:1 No
Ni-2 10405 HMTS LiBArF 2.125 1:1 No
Ni-2 10405 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 10406 HMTS NaEt3BH 2.125 1:1 No
Ni-2 10406 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 10407 HMTS LiBArF 4.25 1:2 No
Ni-2 10407 P SiH3 LiBArF 4.25 1:2 No
Ni-2 10441 HMTS LiBArF 4.25 1:2 No
Ni-2 10441 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 10444 HMTS NaEt3BH 4.25 1:2 No
Ni-2 10444 P SiH3 NaEt3BH 4.25 1:2 No
Ni-2 10445 HMTS LiBArF 4.25 1:2 No
Ni-2 10445 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 10446 HMTS NaEt3BH 2.125 1:1 No
Ni-2 10446 P SiH3 NaEt3BH 2.125 1:1 Yes
Ni-2 10447 HMTS LiBArF 2.125 1:1 No
Ni-2 10447 P SiH3 LiBArF 2.125 1:1 Yes
Ni-2 10450 HMTS LiBArF 4.25 1:2 No
Ni-2 10450 P SiH3 LiBArF 4.25 1:2 Yes
Ni-2 10451 HMTS NaEt3BH 4.25 1:2 No
Ni-2 10451 P SiH3 NaEt3BH 4.25 1:2 Yes
Ni-2 10452 HMTS LiBArF 4.25 1:2 No
Ni-2 10452 P SiH3 LiBArF 4.25 1:2 Yes Metal Ligand Silane Activating Ligand Metal :ligand Catalytically PiecLiisoi Agent Miciomoles Ratio Active? Ni-2 10453 HMTS NaEt3BH 4.25 1 :2 Yes
Ni-2 10453 PhSiH3 NaEt3BH 4.25 1 :2 Yes
Ni-2 10454 HMTS LiBArF 4.25 1 :2 No
Ni-2 10454 PhSiH3 LiBArF 4.25 1 :2 Yes
Ni-2 10455 HMTS NaEt3BH 4.25 1 :2 No
Ni-2 10455 PhSiH3 NaEt3BH 4.25 1 :2 Yes
Ni-2 10456 HMTS LiBArF 4.25 1 :2 No
Ni-2 10456 PhSiH3 LiBArF 4.25 1 :2 Yes
Ni-2 10457 HMTS NaEt3BH 4.25 1 :2 No
Ni-2 10457 PhSiH3 NaEt3BH 4.25 1 :2 Yes
[0241 ] In Table 5, Ni-1 was Nickel (II) bromide dimethoxyethane, and Ni-2 was Nickel (II) bis trimethylsilyl amide.

Claims

1 . A method comprising:
(1 ) combining ingredients comprising an Ni precursor and a ligand, thereby preparing reaction product, where
the Ni precursor has formula (i) N1-A2, where each A is independently a monovalent organic group containing at least one halogen atom, and
the ligand is one of
a compound of general formula (xi)
Figure imgf000099_0001
, where subscript x is an integer from 0 to 2, subscripts y and z are each independently an integer from 0 to 1 , dashed lines indicate single or double bonds, Q50 is selected from N and C, with the proviso that the two N atoms may be positively charged with a balancing negatively charged anion, A86 and each A89 are each independently selected from a monovalent organic group, hydrogen, or an inorganic heteroatom containing group, with the proviso that A86 may not contain thiol or phenyl di-isopropyl, A87 A88, A9^, and A91 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group, and with the provisos that A88 and A90 may be bonded together to form a ring structure, A87 and A88 may be bonded together to form a ring structure, A87 and A86 may be bonded together to form a ring structure, A86 and A91 may be bonded together to form a ring structure, A91 and A90 may be bonded together to form a ring structure; or
Figure imgf000099_0002
2. A method comprising: (1 ) combining ingredients comprising an Ni precursor and a ligand, thereby preparing a reaction product, where
the Ni precursor has formula (i) N1-A2, where each A is independently a monovalent organic group containing at least one silicon atom, and
the ligand is one of general formula (ii), general formula (iv), general formula (vi), general formula (vii), general formula (viii), general formula (ix), general formula (x), general formula (xi), or general formula (xvi); where
Figure imgf000100_0001
general formula (ii) is , where subscript x is an integer from 0 to 1 , Q1 is selected from oxygen, sulphur, nitrogen and phosphorus, A1 , A3, A4, A5, and
A6 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A6 is not chlorobenzene, A2 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the provisos that A2 and A3 may bond together to form a ring structure; A3 and A4 may bond together to form a ring structure; A4 and A5 may bond together to form a ring structure; A5 and A6 may bond together to form a ring str
general formula (iv) is
Figure imgf000100_0002
, subscript x is an integer from 0 to 1 , Q3 is selected from oxygen, sulphur, and nitrogen, A15, A16, A1 7, A1 3, A2^, and A21 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A1 9 is independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A19 does not contain diphenylphosphine, A20 and
A21 can be bonded together to form a ring structure; with the provisos that A1 9 and A1 8 can be bonded together to form a ring structure, A1 8 and A1 7 can be bonded together to form a ring structure, A1 7 and A1 6 can be bonded together to form a ring structure, A1 6 and A1 5 can be bonded together to form a ring structure, ; or
general formula (vi) is
Figure imgf000101_0001
, where subscript x is an integer from 0 to 1 , Q8 is selected from N, O, P, and S, A45, A46, A47, A49, A50, A51 , and A52 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that when Q8 is sulphur then
A45 is not benzene, A48 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; with the provisos that A45 and A52 may combine to form a ring structure, A^2 and may combine to form a ring structure, A^1 and A^O may combine to form a ring structure, A^O and A49 may combine to form a ring structure,
A45 and A4^ may combine to form a ring structure, ; or
general formula (vii) is
Figure imgf000101_0002
_ where subscript x is an integer from 0 to
1 , a dashed line indicates a single or double bond, A56 and A57 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A58 and A55 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A56 and A^7 may combine to form a ring structure, and A^5 and A^6 may combine to form a ring structure, ; or general formula (viii) is
Figure imgf000102_0001
, subscript x is an integer from 0 to
1 , subscript y is an integer from 0 to 1 , Q1 1 and Q1 2 are each independently selected from N, O, P, and S, with the proviso that if Q1 1 or Q1 2 are nitrogen then they are not imine nitrogen, dashed lines represent either single or double bonds, A^O, A^1 , /\β5, and A66 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A62, each A63, and each A64 are independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group; with the provisos that A60 and A61 may be bonded together to form a ring structure, A61 and A62 may be bonded together to form a ring structure, A^2 and A^ may be bonded together to form a ring structure, A^ and A^4 may be bonded together to form a ring structure, A64 and A65 may be bonded together to form a ring structure, A65 and A66 may be bonded together to form a ring structure, A63 and A61 may be bonded together to form a ring structure, ; or
general formula (ix) is
Figure imgf000102_0002
, subscript x is an integer from 0 to 1 , Q1 is selected from N, O, P, and S, and C, with the proviso that when Q17 is C, the carbon forms a carbonyl bond with A31 and a hydroxyl group with A ^ , Q1 3 is selected from O and S, Q1 9 is selected from hydroxyl and thiol. A32, A33, A34, and A35 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A30 and A31 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; with the provisos that A31 and A32 may bond together to form a ring structure, A32 and A33 may bond together to form a ring structure, A33 and A34 may bond together to form a ring structure, A34 and A35 may bond together to form a ring structure, ; or general formula (x) is
Figure imgf000103_0001
, subscript x is an integer from 0 to 1 , Q1 6 is selected from N, O, P, and S, Q1 4 is selected from oxygen and sulphur, Q1 5 is selected from hydroxyl and thiol, each A7^ jS independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group, A77 and A78 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A76 and A77 may bond together to form a ring structure, and A77 and A78 may bond together to form a ring structure, ; or
a compound of general formula (xi)
Figure imgf000103_0002
, where subscript x is an integer from 0 to 2, subscripts y and z are each independently an integer from 0 to 1 , dashed lines indicate single or double bonds, Q50 is selected from N and C, with the proviso that the two N atoms may be positively charged with a balancing negatively charged anion, A86 and each A89 are each independently selected from a monovalent organic group, hydrogen, or an inorganic heteroatom containing group, with the proviso that A86 may not contain thiol or phenyl di-isopropyl, A87 A88, A90, and A91 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group, and with the provisos that A88 and A90 may be bonded together to form a ring structure, A87 and A88 may be bonded together to form a ring structure, A87 and A86 may be bonded together to form a ring structure, A86 and A91 may be bonded together to form a ring structure, A91 and A90 may be bonded together to form a ring structure; or
general formula (xvi) is
Figure imgf000104_0001
' subscripts x and y are each independently integers from 0 to 4, Q24 and Q25 are each independently selected from O and S, subscript z is an integer from 0 to 1 , each A1 20 is independently selected from a monovalent organic group, hydrogen, halogen, and inorganic heteroatom containing group, and A1 21 and A1 22 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group.
3. The method of claim 2, where at least one of the following conditions is satisfied: The ligand has general formula (ii), and the ligand is 8945 in Table 2; or
The ligand has general formula (iv), and the ligand is selected from the group consisting of ligands 7496 and 10132 in Table 2; or
The ligand has general formula (vi), and the ligand is selected from the group consisting of ligands 7534, in Table 2; or
The ligand has general formula (vii), and the ligand is selected from the group consisting of ligands 1936, 2956 and 9072 in Table 2; or
The ligand has general formula (viii), and the ligand is selected from the group consisting of ligands 7534 and 9072 in Table 2; or
The ligand has general formula (ix), and the ligand is selected from the group consisting of ligands 3500 in Table 2; or
The ligand has general formula (x), and the ligand is selected from the group consisting of ligands 2806 in Table 2; or
The ligand has general formula (xi), and the ligand is selected from the group consisting of ligands 8538 in Table 2; or
The ligand has general formula (xvi), and the ligand is selected from the group consisting of ligands 4548 in Table 2.
4. The method of any one of claims 1 - 3, further comprising (2) combining an ionic activator with the reaction product. (LiBArF)
A method comprising: (1 ) combining ingredients comprising an Ni precursor and a ligand, thereby preparing a reaction product, where
the Ni precursor has formula (i) N1-A2, where each A is independently a monovalent organic group containing at least one halogen atom, and
the ligand is one of general formula (ii), general formula (iii), general formula (iv), general formula (vi), general formula (vii), general formula (viii), general formula (xii), or ge
Figure imgf000105_0001
, where subscript x is an integer from 0 to 1 , Q1 is selected from oxygen, sulphur, nitrogen and phosphorus, A1 , A3, A4, A5, and A6 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A6 is not chlorobenzene, A2 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the provisos that A2 and A3 may bond together to form a ring structure; A3 and A4 may bond together to form a ring structure; A4 and A5 may bond together to form a ring structure; A5 and A6 may bond together to form a ring str
general formula (iii) is
Figure imgf000105_0002
, where Q2 is oxygen or sulphur,
A7, A3, Α^, A10, and A12 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A1 1 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that A1 1 is not benzyl, and with the provisos that A7 and A3 may combine to form a ring structure; A3 and A^ may combine to form a ring structure; A9 and A10 may combine to form a ring structure; and A1 1 and A1 2 may combine to form a ring structure, ; or
general formula (iv) is
Figure imgf000106_0001
, subscript x is an integer from 0 to 1 , Q3 is selected from oxygen, sulphur, and nitrogen, A15, A16, A1 7, A1 8, A20, and A21 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A1 9 is independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A19 does not contain diphenylphosphine, A20 and
A21 can be bonded together to form a ring structure; with the provisos that A1 9 and A1 8 can be bonded together to form a ring structure, A1 8 and A1 7 can be bonded together to form a ring structure, A1 7 and A1 6 can be bonded together to form a ring structure, A1 6 and A1 5 can be bonded together to form a ring structure, ; or
general formula (vi) is
Figure imgf000106_0002
, where subscript x is an integer from 0 to 1 , Q8 is selected from N, O, P, and S, A45, A46, A47, A49, A50, A51 , and A52 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that when Q8 is sulphur then A45 is not benzene, A48 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; with the provisos that A45 and A52 may combine to form a ring structure, A^2 and may combine to form a ring structure, A^1 and A^O may combine to form a ring structure, A^O and A49 may combine to form a ring structure, A45 and A4^ may combine to form a ring structure, ; or general formula (vii) is
Figure imgf000107_0001
, where subscript x is an integer from 0 to
1 , a dashed line indicates a single or double bond, A56 and A57 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A58 and A55 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A56 and A57 may combine to form a ring structure, and A^5 and A^6 may combine to form a ring structure, ; or
Figure imgf000107_0002
general formula (viii) is , subscript x is an integer from 0 to
1 , subscript y is an integer from 0 to 1 , Q1 1 and Q1 2 are each independently selected from N, O, P, and S, with the proviso that if Q1 1 or Q12 are nitrogen then they are not imine nitrogen, dashed lines represent either single or double bonds, A^O, A^1 , / δ^ anc| β6 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A62, each A63, and each A64 are independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group; with the provisos that A60 and A61 may be bonded together to form a ring structure, A61 and A62 may be bonded together to form a ring structure, A62 and A63 may be bonded together to form a ring structure, A63 and A64 may be bonded together to form a ring structure, A64 and A65 may be bonded together to form a ring structure, A65 and A66 may be bonded together to form a ring structure, A63 an 61 may be bonded together to form a ring structure, ; or
Figure imgf000107_0003
, subscript x is an integer from 1 to 5, Q20 is selected from N and P, dashed lines indicate a single or double bond, A^O, A^1 , A^2, A^3 A94, and A95 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that when Q20 is nitrogen and A95 is hydrogen then A90 and A91 are not cyclohexyl, and with the proviso that A90 and A91 are not be di(tert-butyl) phenol; with the provisos that A90 and A91 may be bonded together to form a ring structure, with the proviso that when the ring is a phosphalane ring, then A92 and A93 form a phenyl group. Alternatively, A91 and A92 may be bonded together to form a ring structure, A92 and A93 may be bonded together to form a ring structure with the proviso that when Q20 is nitrogen then the ring structure is not indene, A93 and A94 may be bonded together to form a ring structure with the proviso that when Q20 is nitrogen then there are no other hetero-atoms in the ring structure with Q20, A94 and A95 may be bonded together to form a ring structure, and with the proviso that when subscript x is 2 or more, then two or more instances of A93 may bond together to form a ring structure; or
general formula (xiii) is
Figure imgf000108_0001
, subscript x is an integer from 0 to 1 , Q21 is selected from N, O, P, and S, A96, A97, A98, A99, A1 00, A1 01 , A1 02 A1 03, A1 04, A105j A106, A107, and A108 are each independently selected from a monovalent organic group, hydrogen, a halogen, and an inorganic heteroatom containing group; with the provisos that A9^ and A97 may bond together to form a ring structure, A99 and A100 may bond together to form a ring structure, A96 and A1 °8 may bond together to form a ring structure, A108 and A107 may bond together to form a ring structure, A107 and A106 may bond together to form a ring structure, A1 °6 anc| A105 may bond together to form a ring structure, A1 °5 anc| A104 may bond together to form a ring structure, with the proviso that the bridging atom is not N in an amine group, and with the provisos that A104 and A103 may bond together to form a ring structure, A1 °3 anc| A102 may bond together to form a ring structure, A1 02 and A1 °1 may bond together to form a ring structure.
6. The method of claim 5, where at least one of the following conditions is satisfied:
The ligand has general formula (ii), and the ligand is selected from the group consisting of ligands 510, 8838, 8856, and 8945 in Table 2; or
The ligand has general formula (iii), and the ligand is selected from the group consisting of ligands 10364 in Table 2; or
The ligand has general formula (iv), and the ligand is selected from the group consisting of ligands 3746, 10132, and 10218 in Table 2; or
The ligand has general formula (vi), and the ligand is selected from the group consisting of ligands 2272 in Table 2; or
The ligand has general formula (vii), and the ligand is selected from the group consisting of ligands 1936, 2956 and 6417 in Table 2; or
The ligand has general formula (viii), and the ligand is selected from the group consisting of ligands 3746 in Table 2; or
The ligand has general formula (xii), and the ligand is selected from the group consisting of ligands 10394 in Table 2; or
The ligand has general formula (xiii), and the ligand is selected from the group consisting of ligands 10405 in Table 2.
7. A method comprising:
(1 ) combining ingredients comprising an Ni precursor and a ligand, thereby preparing a reaction product, where
the Ni precursor has formula (i) N1-A2, where each A is independently a monovalent organic group containing at least one silicon atom, and
the ligand is one of general formula (ii), general formula (iii), general formula (iv), general formula (v), general formula (vi), general formula (vii), general formula (viii), general formula (xi), general formula (xii), general formula (xv), general formula (xviii), and general formula (xix), whe
general formula (ii) is
Figure imgf000109_0001
, where subscript x is an integer from 0 to 1 , Q1 is selected from oxygen, sulphur, nitrogen and phosphorus, A1 , A3, A4, A5, and A6 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A6 is not chlorobenzene, A2 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the provisos that A2 and A3 may bond together to form a ring structure; A3 and A4 may bond together to form a ring structure; A4 and A5 may bond together to form a ring structure; A5 and A6 may bond together to form a ring structure, ; or
general formula (iii) is
Figure imgf000110_0001
, where Q2 is oxygen or sulphur,
A7, A3, A9, A10, and A1 2 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A1 1 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that A1 1 is not benzyl, and with the provisos that A7 and A3 may combine to form a ring structure; A3 and A9 may combine to form a ring structure; A9 and A1 ^ may combine to form a ring structure; and A1 1 and A1 2 may combine to form a ring str
general formula (iv) is
Figure imgf000110_0002
, subscript x is an integer from 0 to 1 , Q3 is selected from oxygen, sulphur, and nitrogen, A15, A16, A1 7, A1 3, A2^, and A21 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A1 9 is independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A19 does not contain diphenylphosphine, A20 and
A21 can be bonded together to form a ring structure; with the provisos that A1 9 and A1 3 can be bonded together to form a ring structure, A1 8 and A1 7 can be bonded together to form a ring structure, A1 7 and A1 6 can be bonded together to form a ring structure, A1 6 and A1 5 can be bonded together to form a ring structure, or;
general formula (v) is
Figure imgf000111_0001
, where subscript x is an integer from 0 to 1 , dashed lines denote either a single or double bond, subscript y is an integer from 0 to 1 , Q4 and Q5 are each independently selected from N, O, P, and S, A25, A26, A27, A28, A29, A30, A81 , and A82 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group; with the provisos that A29 and A25 may be bonded together to form a ring structure, A25 and A26 may be bonded together to form a ring structure, A26 and A27 may be bonded together to form a ring structure, A27 and A28 may be bonded together to form a ring structure, and A28 and A82 may be bonded together to form a ring structure, A29 and A80 may be bonded together to form a ring structure, with the proviso that the ring structure formed by bonding together A29 and A8^ is not pyrrole and A81 and A82 may be bonded together to form a ring structure, with the proviso that the ring structure formed by bonding together
A81 and A82 is not pyrrol
general formula (vi) is
Figure imgf000111_0002
, where subscript x is an integer from 0 to 1 , Q8 is selected from N, O, P, and S, A45, A46, A47, A49, A50, A51 , and A52 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that when Q8 is sulphur then A45 is not benzene, A48 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; with the provisos that A45 and A52 may combine to form a ring structure, A^2 and A^1 may combine to form a ring structure, A^1 and A^O may combine to form a ring structure, A^O and A49 may combine to form a ring structure, A45 and A4^ may combine to form a ring structure; or,
general formula (vii) is
Figure imgf000112_0001
_ where subscript x is an integer from 0 to 1 , a dashed line indicates a single or double bond, A56 and A57 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A58 and A55 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A56 and A57 may combine to form a ring structure, and A^5 and A^6 may combine to form a ring structure; or,
general formula (viii) is
Figure imgf000112_0002
, subscript x is an integer from 0 to
1 , subscript y is an integer from 0 to 1 , Q1 1 and Q1 2 are each independently selected from N, O, P, and S, with the proviso that if Q1 1 or Q12 are nitrogen then they are not imine nitrogen, dashed lines represent either single or double bonds, A^O, A^1 , /\β5, and A66 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A62, each A63, and each A64 are independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group; with the provisos that A60 and A61 may be bonded together to form a ring structure, A61 and A62 may be bonded together to form a ring structure, A^2 and A^3 may be bonded together to form a ring structure, A^3 and A^4 may be bonded together to form a ring structure, A64 and A65 may be bonded together to form a ring structure, A65 and A66 may be bonded together to form a ring structure, A63 and A61 may be bonded together to form a ring structure, a compound of general formula (xi)
Figure imgf000113_0001
, where subscript x is an integer from 0 to 2, subscripts y and z are each independently an integer from 0 to 1 , dashed lines indicate single or double bonds, Q50 is selected from N and C, with the proviso that the two N atoms may be positively charged with a balancing negatively charged anion, A86 and each A89 are each independently selected from a monovalent organic group, hydrogen, or an inorganic heteroatom containing group, with the proviso that A86 may not contain thiol or phenyl di-isopropyl, A87 A88, A9^, and A91 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group, and with the provisos that A88 and A90 may be bonded together to form a ring structure, A87 and A88 may be bonded together to form a ring structure, A87 and A86 may be bonded together to form a ring structure, A86 and A91 may be bonded together to form a ring structure, A91 and A90 may be bonded together to form a ring structure; or
general formula (xii) is
Figure imgf000113_0002
, subscript x is an integer from 1 to 5, Q20 is selected from N and P, dashed lines indicate a single or double bond, A9^, A91 , A92, A98
A94, and A95 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that when Q2^ is nitrogen and A95 is hydrogen then A9^ and A91 are not cyclohexyl, and with the proviso that A90 and A91 are not be di(tert-butyl) phenol; with the provisos that A90 and A91 may be bonded together to form a ring structure, with the proviso that when the ring is a phosphalane ring, then A92 and A93 form a phenyl group. Alternatively, A91 and A92 may be bonded together to form a ring structure, A92 and A93 may be bonded together to form a ring structure with the proviso that when Q2^ is nitrogen then the ring structure is not indene, A98 and A94 may be bonded together to form a ring structure with the proviso that when Q2^ is nitrogen then there are no other hetero-atoms in the ring structure with Q20, A94 and A95 may be bonded together to form a ring structure, and with the proviso that when subscript x is 2 or more, then two or more instances of A93 may bond together to form a ring structure; or,
general formula (xv) is
Figure imgf000114_0001
, where Q22 and Q23 are each independently selected from oxygen and sulphur, and A115, A116, A11 7, and A118 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A116 and A115 may combine to form a ring structure, A118 and A11 9 may combine to form a ring structure; or,
A133
general formula (xviii) is ^132 ^134 , where A132J A133J ANC| A134 are each independently selected from a monovalent organic group, hydrogen, a halogen, or an inorganic heteroatom containing group, and A13 and A135 are independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group.
, and
Figure imgf000114_0002
each A142, each A143, and each A144 are independently selected from a monovalent organic group, hydrogen, halogen, or inorganic group, and A136J A137J A139, and A140 are independently selected from a monovalent organic group, hydrogen, or an inorganic group. 8. The method of claim 7, where at least one of the following conditions is satisfied:
The ligand has general formula (ii), and the ligand is selected from the group consisting of ligands 483, 484, 486, 488, 512, 777, 785, 819, 6269, 8842, and 8946 in Table 2; or The ligand has general formula (iii), and the ligand is selected from the group consisting of ligands 604, 2920, and 2921 in Table 2; or The ligand has general formula (iv), and the ligand is selected from the group consisting of ligands 1430, 1832, 2072, 3749, 5479, and 7124 in Table 2; or
The ligand has general formula (v), and the ligand is selected from the group consisting of ligands 165, 1 125, 1214, 4202, and 8749 in Table 2; or
The ligand has general formula (vi), and the ligand is selected from the group consisting of ligands 635, 1888, 2062, 3096, 4202, 6340, and 7124 in Table 2; or
The ligand has general formula (vii), and the ligand is selected from the group consisting of ligands 732, 2956, and 10267 in Table 2; or
The ligand has general formula (viii), and the ligand is selected from the group consisting of ligands 1214, 1769, 3499, 3547, and 8977 in Table 2; or
The ligand has general formula (xi), and the ligand is selected from the group consisting of ligands 6253, 6340, 8500, 8749, 8977, 10380, and 10390 in Table 2; or
The ligand has general formula (xii), and the ligand is selected from the group consisting of ligands 10404 in Table 2; or
The ligand has general formula (xv), and the ligand is selected from the group consisting of ligands 8768 in Table 2; or
The ligand has general formula (xviii), and the ligand is selected from the group consisting of ligands 10453 in Table 2; or
The ligand has general formula (xix), and the ligand is 10150 in Table 2.
9. The method of any one of claims 5 - 8, further comprising (2) combining the reaction product with a reducing agent. (NaEt3BH from Aldrich)
10. A method comprising:
(1 ) combining ingredients comprising an Ni precursor and a ligand, thereby preparing a reaction product, where
the Ni precursor has formula (i) N1-A2, where each A is independently a monovalent organic group containing at least one halogen atom, and
the ligand is one of general formula (ii), general formula (iii), general formula (iv), general formula (v), general formula (vi), general formula (vii), general formula (viii), general formula (ix), general formula (xi), general formula (xii), general formula (xiii), general formula (xvii), or general formula (xviii), where general formula (ii) is
Figure imgf000116_0001
, where subscript x is an integer from 0 to 1 , Q1 is selected from oxygen, sulphur, nitrogen and phosphorus, A1 , A3, A4,
A5, and A6 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A6 is not chlorobenzene, A2 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the provisos that A2 and A3 may bond together to form a ring structure; A3 and A4 may bond together to form a ring structure; A4 and A5 may bond together to form a ring structure; A5 and A6 may bond together to form a ring structu
general formula (iii) is
Figure imgf000116_0002
_ where Q2 is oxygen or sulphur, A7, A3, A^, A1 ^, and A1 2 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group,
A1 1 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that A1 1 is not benzyl, and with the provisos that A7 and A3 may combine to form a ring structure; A3 and A^ may combine to form a ring structure; A 9 and A1 ^ may combine to form a ring structure; and A1 1 and A1 2 may combine to form a ring structure; or, general formula (iv) is
Figure imgf000117_0001
, subscript x is an integer from 0 to 1 ,
Q8 is selected from oxygen, sulphur, and nitrogen, A15, A16, A1 7, A18, A20, and A21 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A1 9 is independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A19 does not contain diphenylphosphine, A20 and
A21 can be bonded together to form a ring structure; with the provisos that A1 9 and A1 8 can be bonded together to form a ring structure, A1 8 and A1 7 can be bonded together to form a ring structure, A1 7 and A1 6 can be bonded together to form a ring structure, A1 6 and A1 5 can be bonded toge re; or,
general formula (v) is
Figure imgf000117_0002
where subscript x is an integer from
0 to 1 , dashed lines denote either a single or double bond, subscript y is an integer from 0 to 1 , Q4 and Q5 are each independently selected from N, O, P, and S, A25, A26, A27, A28, A29, A30, A81 , and A82 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group; with the provisos that A29 and A25 may be bonded together to form a ring structure, A25 and A26 may be bonded together to form a ring structure, A26 and A27 may be bonded together to form a ring structure, A27 and A28 may be bonded together to form a ring structure, and A28 and A82 may be bonded together to form a ring structure, A29 and A80 may be bonded together to form a ring structure, with the proviso that the ring structure formed by bonding together A29 and A8^ is not pyrrole and A81 and A82 may be bonded together to form a ring structure, with the proviso that the ring structure formed by bonding together A81 and A82 jS not pyrrole; or,
general formula (vi) is
Figure imgf000118_0001
_ where subscript x is an integer from 0 to 1 , Q8 is selected from N, O, P, and S, A45, A46, A47, A49, A50, A51 , and A52 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that when Q8 is sulphur then A4^ is not benzene, A48 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; with the provisos that A45 and A52 may combine to form a ring structure, A^2 and A^1 may combine to form a ring structure, A^1 and A^O may combine to form a ring structure, A^O and A49 may combine to form a ring structure, A45 and A46 may combine to form a ring structure; or,
general formula (vii) is
Figure imgf000118_0002
_ where subscript x is an integer from
0 to 1 , a dashed line indicates a single or double bond, A56 and A57 are each
independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A58 and A55 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that
A56 and A^7 may combine to form a ring structure, and A^5 and A^6 may combine to form a ring structure; or,
Figure imgf000118_0003
general formula (viii) is , subscript x is an integer from 0 to 1 , subscript y is an integer from 0 to 1 , Q1 1 and Q12 are each independently selected from N, O, P, and S, with the proviso that if Q1 1 or Q12 are nitrogen then they are not imine nitrogen, dashed lines represent either single or double bonds, A^O, A^1 , A^ and
A66 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A62, each A63, and each A64 are independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group; with the provisos that A60 and A61 may be bonded together to form a ring structure, A61 and A62 may be bonded together to form a ring structure, A62 and A63 may be bonded together to form a ring structure, A63 and A64 may be bonded together to form a ring structure, A64 and A65 may be bonded together to form a ring structure, A65 and A66 may be bonded together to form a ring structure, A63 and A61 may be bonded together to form a ring structure,
general formula (ix) is
Figure imgf000119_0001
, subscript x is an integer from 0 to 1 ,
Q1 7 is selected from N, O, P, and S, and C, with the proviso that when Q17 is C, the carbon forms a carbonyl bond with A31 and a hydroxyl group with A30 , Q18 is selected from O and S, Q1 9 is selected from hydroxyl and thiol. A32, A33, A34, and A35 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A30 and A31 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; with the provisos that A31 and A32 may bond together to form a ring structure, A32 and A33 may bond together to form a ring structure, A33 and A34 may bond together to form a ring structure, A34 and A35 may bond together to form a ring structure; or,
a compound of general formula (xi)
Figure imgf000119_0002
, where subscript x is an integer from 0 to 2, subscripts y and z are each independently an integer from 0 to 1 , dashed lines indicate single or double bonds, Q50 is selected from N and C, with the proviso that the two N atoms may be positively charged with a balancing negatively charged anion, A86 and each A89 are each independently selected from a monovalent organic group, hydrogen, or an inorganic heteroatom containing group, with the proviso that A86 may not contain thiol or phenyl di-isopropyl, A87 A88, A9^, and A91 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group, and with the provisos that A88 and A90 may be bonded together to form a ring structure, A87 and A88 may be bonded together to form a ring structure, A87 and A86 may be bonded together to form a ring structure, A86 and A91 may be bonded together to form a ring structure, A91 and A90 may be bonded together to form a ring structure; or
Λ 90 Λ 91
general formula (xii) is
Figure imgf000120_0001
_ subscript x is an integer from 1 to 5, Q20 is selected from N and P, dashed lines indicate a single or double bond, A90, A91 , A92,
A93 A94, and A95 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that when Q2^ is nitrogen and A9^ is hydrogen then A9^ and A91 are not cyclohexyl, and with the proviso that A90 and A91 are not be di(tert-butyl) phenol; with the provisos that
A90 and A91 may be bonded together to form a ring structure, with the proviso that when the ring is a phosphalane ring, then A92 and A98 form a phenyl group. Alternatively, A91 and A92 may be bonded together to form a ring structure, A92 and A93 may be bonded together to form a ring structure with the proviso that when Q20 is nitrogen then the ring structure is not indene, A93 and A94 may be bonded together to form a ring structure with the proviso that when Q2^ is nitrogen then there are no other hetero-atoms in the ring structure with Q20, A94 and A95 may be bonded together to form a ring structure, and with the proviso that when subscript x is 2 or more, then two or more instances of A93 may bond together to form a ring structure; or, general formula (xiii) is
Figure imgf000121_0001
, subscript x is an integer from 0 to 1 , Q21 is selected from N, O, P, and S, A96, A97, A98, A99, A1 00, A1 01 , A1 02
A 03, A 04, A 05, A 06, A °7, and A 08 are each independently selected from a monovalent organic group, hydrogen, a halogen, and an inorganic heteroatom containing group; with the provisos that A96 and A97 may bond together to form a ring structure, A99 and A1 00 may bond together to form a ring structure, A96 and A1 08 may bond together to form a ring structure, A108 and A1 07 may bond together to form a ring structure, A1 07 and A1 06 may bond together to form a ring structure, A1 06 and A1 05 may DOrid together to form a ring structure, A105 ANC| A1 04 may Donc| together to form a ring structure, with the proviso that the bridging atom is not N in an amine group, and with the provisos that A1 °4 and A1 03 may Donc| together to form a ring structure, A1 03 ANC| A1 02 may Donc| together d together to form a ring structure; or,
Figure imgf000121_0002
where Q26 is selected from O and S,
Q27 is selected from N and C, subscript x is an integer from 0 to 4, A125, A126, A127, A1 28, and A1 30 are each independently selected from a monovalent organic group, hydrogen, a halogen, or an inorganic heteroatom containing group, and A1 29 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group, with the proviso that A12 form a ring structure; or
general formula (xviii) is
Figure imgf000121_0003
where A1 32, A1 33, and A1 34 are each independently selected from a monovalent organic group, hydrogen, a halogen, or an inorganic heteroatom containing group, and A131 and A135 are independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group. 1 1. The method of claim 10, where one of the following conditions is satisfied:
The ligand has general formula (ii), and the ligand is selected from the group consisting of ligands 483, 486, 488, 777, 785, 819, 6269, and 8842 in Table 2; or
The ligand has general formula (iii), and the ligand is selected from the group consisting of ligands 604, 2920, 2921 , and 7377 in Table 2; or
The ligand has general formula (iv), and the ligand is selected from the group consisting of ligands 1430, 2072, 3749, and 7124 in Table 2; or
The ligand has general formula (v), and the ligand is selected from the group consisting of ligands 819, 1 125, 1214, and 4202, in Table 2; or
The ligand has general formula (vi), and the ligand is selected from the group consisting of ligands 635, 1888, 2061 , 2062, 3096, 4202, 4990, 6253, 6340, and 7124 in Table 2; or
The ligand has general formula (vii), and the ligand is selected from the group consisting of ligands 734 and 2956 in Table 2; or
The ligand has general formula (viii), and the ligand is selected from the group consisting of ligands 1214, 3499, 3749, and 8977 in Table 2; or
The ligand has general formula (ix), and the ligand is selected from the group consisting of ligands 2816 in Table 2; or
The ligand has general formula (xi), and the ligand is selected from the group consisting of ligands 6253, 6340, 8500, 8977, 10374, 10377, 10380, and 10390 in Table 2; or
The ligand has general formula (xii), and the ligand is selected from the group consisting of ligands 10386 in Table 2; or
The ligand has general formula (xiii), and the ligand is selected from the group consisting of ligands 10446 in Table 2; or
The ligand has general formula (xvii), and the ligand is selected from the group consisting of ligands 10444 in Table 2; or
The ligand has general formula (xviii), and the ligand is selected from the group consisting of ligands 10453 in Table 2.
A method comprising: (1 ) combining ingredients comprising an Ni precursor and a ligand, thereby preparing a reaction product, where
the Ni precursor has formula (i) N1-A2, where each A is independently a monovalent organic group containing at least one silicon atom, and
the ligand is one of general formula (ii), general formula (iii),general formula (iv), general formula (v), general formula (vi), general formula (vii), general formula (viii), general formula (ix), general formula (x), general formula (xi), general formula (xii), general formula (xiii), general formula (xiv), general formula (xv), general formula (xvi), or general formula (xvii), where
general formula (ii) is
Figure imgf000123_0001
, where subscript x is an integer from 0 to 1 , Q1 is selected from oxygen, sulphur, nitrogen and phosphorus, A1 , A3, A4, A5, and
A6 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A6 is not chlorobenzene, A2 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the provisos that A2 and A3 may bond together to form a ring structure; A3 and A4 may bond together to form a ring structure; A4 and A5 may bond together to form a ring structure; A5 and A6 may bond together to form a ring str
general formula (iii) is
Figure imgf000123_0002
_ where Q2 is oxygen or sulphur,
A7, A3, Α^, A10, and A1 2 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A1 1 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that A1 1 is not benzyl, and with the provisos that A7 and A8 may combine to form a ring structure; A8 and A9 may combine to form a ring structure; A9 and A10 may combine to form a ring structure; and A1 1 and A1 2 may combine to form a ring structure; or,
general formula (iv) is
Figure imgf000124_0001
, subscript x is an integer from 0 to 1 , Q3 is selected from oxygen, sulphur, and nitrogen, A1 5, A1 6, A1 7, A1 8, A20, and A21 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A1 9 is independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A19 does not contain diphenylphosphine, A20 and A21 can be bonded together to form a ring structure; with the provisos that A1 9 and A1 8 can be bonded together to form a ring structure, A1 8 and A1 7 can be bonded together to form a ring structure, A1 7 and A1 6 can be bonded together to form a ring structure, A1 6 and A1 5 can be bonded together to form a ring structure; or,
general formula (v) is
Figure imgf000124_0002
, where subscript x is an integer from 0 to 1 , dashed lines denote either a single or double bond, subscript y is an integer from 0 to 1 , Q4 and Q5 are each independently selected from N, O, P, and S, A25, A26, A27, A28,
A29, A80, A81 , and A82 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group; with the provisos that A29 and A25 may be bonded together to form a ring structure, A25 and A26 may be bonded together to form a ring structure, A26 and A27 may be bonded together to form a ring structure, A27 and A28 may be bonded together to form a ring structure, and
A28 and A82 may be bonded together to form a ring structure, A29 and A ^ may be bonded together to form a ring structure, with the proviso that the ring structure formed by bonding together A2^ and A^O is not pyrrole and A81 and A82 may be bonded together to form a ring structure, with the proviso that the ring structure formed by bonding together A81 and A82 is not pyrrole; or,
general formula (vi) is
Figure imgf000125_0001
_ where subscript x is an integer from 0 to 1 , Q8 is selected from N, O, P, and S, A45, A46, A47, A49, A50, A51 , and 2 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that when Q8 is sulphur then A4^ is not benzene, A48 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; with the provisos that A45 and A^2 may combine to form a ring structure, A^2 and A^1 may combine to form a ring structure, and A^O may combine to form a ring structure, A^O and A4^ may combine to form a ring structure, A45 and A46 may combine to form a ring structure; or,
general formula (vii) is
Figure imgf000126_0001
, where subscript x is an integer from
0 to 1 , a dashed line indicates a single or double bond, A56 and A57 are each
independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A58 and A55 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A56 and A^7 may combine to form a ring structure, and A^5 and A^6 may combine to form a ring structure; or
Figure imgf000126_0002
general formula (viii) is , subscript x is an integer from 0 to 1 , subscript y is an integer from 0 to 1 , Q1 1 and Q1^ are each independently selected from N, O, P, and S, with the proviso that if Q1 1 or Q1 2 are nitrogen then they are not imine nitrogen, dashed lines represent either single or double bonds, A^O, A^1 , A^ and A66 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A62, each A63, and each A64 are independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group; with the provisos that A60 and A61 may be bonded together to form a ring structure, A61 and A62 may be bonded together to form a ring structure, A62 and A63 may be bonded together to form a ring structure, A63 and A64 may be bonded together to form a ring structure, A64 and A65 may be bonded together to form a ring structure, A65 and A66 may be bonded together to form a ring structure, A63 and A61 may be bonded together to form a ring structure; or, general formula (ix) is
Figure imgf000127_0001
, subscript x is an integer from 0 to 1 ,
Q1 7 is selected from N, O, P, and S, and C, with the proviso that when Q17 is C, the carbon forms a carbonyl bond with A81 and a hydroxyl group with A80 , Q1 8 is selected from O and S, Q1 ^ is selected from hydroxyl and thiol. A82, A83, A84, and A8^ are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A80 and A81 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; with the provisos that A81 and A82 may bond together to form a ring structure, A82 and A83 may bond together to form a ring structure, A83 and A84 may bond together to form a ring structure, A84 an 85 may bond together to form a ring structure; or
general formula (x) is
Figure imgf000127_0002
, subscript x is an integer from 0 to 1 ,
Q1 6 is selected from N, O, P, and S, Q1 4 is selected from oxygen and sulphur, Q1 5 is selected from hydroxyl and thiol, each A7^ is independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group, A77 and A78 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A76 and A77 may bond together to form a ring structure, and A77 and A78 may bond together to form a ring structure; or,
a compound of general formula (xi)
Figure imgf000127_0003
, where subscript x is an integer from 0 to 2, subscripts y and z are each independently an integer from 0 to 1 , dashed lines indicate single or double bonds, Q50 is selected from N and C, with the proviso that the two N atoms may be positively charged with a balancing negatively charged anion, A86 and each A89 are each independently selected from a monovalent organic group, hydrogen, or an inorganic heteroatom containing group, with the proviso that A86 may not contain thiol or phenyl di-isopropyl, A87 A88, A9^, and A91 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group, and with the provisos that A88 and A90 may be bonded together to form a ring structure, A87 and A88 may be bonded together to form a ring structure, A87 and A86 may be bonded together to form a ring structure, A86 and A91 may be bonded together to form a ring structure, A91 and A90 may be bonded together to form a ring structure; or
general formula (xii) is
Figure imgf000128_0001
, subscript x is an integer from 1 to 5, Q20 is selected from N and P, dashed lines indicate a single or double bond, A9^, A91 , A92, A98
A94, and A95 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that when Q2^ is nitrogen and A9^ is hydrogen then A9^ and A91 are not cyclohexyl, and with the proviso that A90 and A91 are not be di(tert-butyl) phenol; with the provisos that
A90 and A91 may be bonded together to form a ring structure, with the proviso that when the ring is a phosphalane ring, then A92 and A98 form a phenyl group. Alternatively, A91 and A92 may be bonded together to form a ring structure, A92 and A93 may be bonded together to form a ring structure with the proviso that when Q2^ is nitrogen then the ring structure is not indene, A98 and A94 may be bonded together to form a ring structure with the proviso that when Q20 is nitrogen then there are no other hetero-atoms in the ring structure with Q20, A94 and A95 may be bonded together to form a ring structure, and with the proviso that when subscript x is 2 or more, then two or more instances of A98 may bond together to form a ring structure; or, general formula (xiii) is
Figure imgf000129_0001
, subscript x is an integer from
0 to 1 , Q21 is selected from N, O, P, and S, A96, A97, A98, A99, A1 00, A1 01 , A1 02, A1 03, A104, A105j A106, A1 07, and A108 are each independently selected from a monovalent organic group, hydrogen, a halogen, and an inorganic heteroatom containing group; with the provisos that A96 and A97 may bond together to form a ring structure, A99 and A100 may bond together to form a ring structure, A96 and A1 °8 may Donc| together to form a ring structure, A108 anc| A107 may Donc| together to form a ring structure, A107 anc| A106 may bond together to form a ring structure, A1 °6 anc| A105 may Donc| together to form a ring structure, A1 °5 anc| A104 may Donc| together to form a ring structure, with the proviso that the bridging atom is not N in an amine group, and with the provisos that A104 anc| A103 may bond together to form a ring structure, A1 °3 anc| A102 may Donc| together to form a ring structure, A1 02 and A1 °1 may bond together to form a ring structure; or,
general formula (xiv) '
Figure imgf000129_0002
, where subscripts x and y are each independently an integer from 0 to 5, and A1 1 1 , A1 1 °, and A1 1 2 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group; or,
general formula (xv) is
Figure imgf000129_0003
_ where Q22 and Q23 are each independently selected from oxygen and sulphur, and A1 15, A1 16, A1 1 7, and A1 1 3 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A1 16 and A1 15 may combine to form a ring structure, A1 1 and A1 1 9 may combine to form a ring structure; or general formula (xvi) is
Figure imgf000130_0001
' subscripts x and y are each independently integers from 0 to 4, Q24 and Q25 are each independently selected from O and S, subscript z is an integer from 0 to 1 , each A1 20 is independently selected from a monovalent organic group, hydrogen, halogen, and inorganic heteroatom containing group, and A1 21 and A1 22 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; or
general formula (xvii)
Figure imgf000130_0002
is selected from O and S, Q27 is selected from N and C, subscript x is an integer from 0 to 4, A1 25, A1 26, A127, A1 28, and A1 30 are each independently selected from a monovalent organic group, hydrogen, a halogen, or an inorganic heteroatom containing group, and A1 29 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group, with the proviso that A1 28 and A1 29 may combine to form a ring structure.
13. The method of claim 12, where one of the following conditions is satisfied:
The ligand has general formula (ii), and the ligand is selected from the group consisting of ligands 484, 510, 8838, 8856, and 8945 in Table 2; or
The ligand has general formula (iii), and the ligand is selected from the group consisting of ligands 6886, 7282, and 10364 in Table 2; or The ligand has general formula (iv), and the ligand is selected from the group consisting of ligands 755, 1483, 2915, 2927, 3472, 3746, 4098, 41 17, 6870, 7471 , 7496, and 10132 in Table 2; or
The ligand has general formula (v), and the ligand is selected from the group consisting of ligands 788, 799, 805, 1 1 16, 1547, and 3544 in Table 2; or
The ligand has general formula (vi), and the ligand is selected from the group consisting of ligands 1249, 2075, 2272, 3191 , 5177, 6322, 6372, and 7534 in Table 2; or
The ligand has general formula (vii), and the ligand is selected from the group consisting of ligands 735, 1936, 2956, 6417, and 9042 in Table 2; or
The ligand has general formula (viii), and the ligand is selected from the group consisting of ligands 748, 3746, 6322, 6372, 7534, 8881 , 9042, and 9072 in Table 2; or
The ligand has general formula (ix), and the ligand is selected from the group consisting of ligands 3500 in Table 2; or
The ligand has general formula (x), and the ligand is selected from the group consisting of ligands 2806 in Table 2; or
The ligand has general formula (xi), and the ligand is selected from the group consisting of ligands 8538, 8881 , 9042, 10376, 10379, 10381 , 10390, 10450, 10452, 10454, and 10456 in Table 2; or
The ligand has general formula (xii), and the ligand is selected from the group consisting of ligands 10383, 10385, 10387, 10389, 10392, 10398, 10400, and 10447 in Table 2; or
The ligand has general formula (xiii), and the ligand is selected from the group consisting of ligands 10405 in Table 2; or
The ligand has general formula (xiv), and the ligand is selected from the group consisting of ligands 3179 in Table 2; or
The ligand has general formula (xv), and the ligand is selected from the group consisting of ligands 4570 in Table 2; or
The ligand has general formula (xvi), and the ligand is selected from the group consisting of ligands 4548 in Table 2; or
The ligand has general formula (xvii), and the ligand is selected from the group consisting of ligands 10441 and 10445 in Table 2.
14. The method of any one of claims 10 - 13, further comprising (2) combining the reaction product with an ionic activator.
15. A method comprising: (1 ) combining ingredients comprising an Ni precursor and a ligand, thereby preparing a reaction product, where
the Ni precursor has formula (i) N1-A2, where each A is independently a monovalent organic group containing at least one halogen atom, and
the ligand is one of general formula (ii), general formula (iii), general formula (iv), general formula (v), general formula (vi), general formula (vii), general formula (viii), general formula (ix), general formula (x), general formula (xi), general formula (xii), general formula (xiii), general formula (xiv), general formula (xv), general formula (xvi), or general formula (xvii), where
general formula (ii) is
Figure imgf000132_0001
, where subscript x is an integer from 0 to 1 , Q1 is selected from oxygen, sulphur, nitrogen and phosphorus, A1 , A3, A4, A5, and
A6 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A6 is not chlorobenzene, A2 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the provisos that A2 and A3 may bond together to form a ring structure; A3 and A4 may bond together to form a ring structure; A4 and A5 may bond together to form a ring structure; A5 and A6 may bond together to form a ring structure; or,
general formula (iii) is
Figure imgf000133_0001
_ where Q2 is oxygen or sulphur, A7, A8, A9, A1 ^, and A1 2 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group,
A1 1 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that A1 1 is not benzyl, and with the provisos that A7 and A8 may combine to form a ring structure; A8 and A9 may combine to form a ring structure; A9 and A1 0 may combine to form a ring structure; and A1 1 and A1 2 may combine to form a ring structure; or
general formula (iv) is
Figure imgf000133_0002
, subscript x is an integer from 0 to 1 , Q8 is selected from oxygen, sulphur, and nitrogen, A15, A16, A1 7, A1 8, A2^, and A21 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A1 9 is independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A1 9 does not contain diphenylphosphine, A20 and A21 can be bonded together to form a ring structure; with the provisos that A1 9 and A1 8 can be bonded together to form a ring structure, A1 8 and A1 7 can be bonded together to form a ring structure, A1 7 and A1 6 can be bonded together to form a ring structure, A1 6 and A1 5 can be bonded together to form a ring structure; or general formula (v) is
Figure imgf000134_0001
where subscript x is an integer from
0 to 1 , dashed lines denote either a single or double bond, subscript y is an integer from 0 to 1 , Q4 and Q5 are each independently selected from N, O, P, and S, A25, A26, A27, A28, A29, A30J A31 , and A82 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group; with the provisos that A29 and A25 may be bonded together to form a ring structure, A25 and A26 may be bonded together to form a ring structure, A26 and A27 may be bonded together to form a ring structure, A27 and A28 may be bonded together to form a ring structure, and A28 and A82 may be bonded together to form a ring structure, A29 and A^O may be bonded together to form a ring structure, with the proviso that the ring structure formed by bonding together A29 and A^O is not pyrrole and A81 and A82 may be bonded together to form a ring structure, with the proviso that the ring structure formed by bonding together A81 and A82 is not pyrrole; or
general formula (vi) is
Figure imgf000134_0002
_ where subscript x is an integer from 0 to 1 , Q8 is selected from N, O, P, and S, A45, A46, A47, A49, A50, A51 , and A52 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that when Q8 is sulphur then A45 is not benzene, A48 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; with the provisos that A45 and A^2 may combine to form a ring structure, A^2 and A^1 may combine to form a ring structure, and A^O may combine to form a ring structure, A^O and A49 may combine to form a ring structure, A45 and A46 may combine to form a ring structure; or general formula (vii) is
Figure imgf000135_0001
, where subscript x is an integer from
0 to 1 , a dashed line indicates a single or double bond, A56 and A57 are each
independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A58 and A55 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A56 and A^7 may combine to form a ring structure, and A^5 and A^6 may combine to form a ring structure; or
Figure imgf000135_0002
general formula (viii) is , subscript x is an integer from 0 to 1 , subscript y is an integer from 0 to 1 , Q1 1 and Q1 2 are each independently selected from N, O, P, and S, with the proviso that if Q1 1 or Q1 2 are nitrogen then they are not imine nitrogen, dashed lines represent either single or double bonds, A^O, A^1 , A^ and A66 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A62, each A63, and each A64 are independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group; with the provisos that A60 and A61 may be bonded together to form a ring structure, A61 and A62 may be bonded together to form a ring structure, A62 and A63 may be bonded together to form a ring structure, A63 and A64 may be bonded together to form a ring structure, A64 and A65 may be bonded together to form a ring structure, A65 and A66 may be bonded together to form a ring structure, A63 and A61 may be bonded together to form a ring structure. general formula (ix) is
Figure imgf000136_0001
, subscript x is an integer from 0 to 1 ,
Q1 7 is selected from N, O, P, and S, and C, with the proviso that when Q17 is C, the carbon forms a carbonyl bond with A81 and a hydroxyl group with A80 , Q1 8 is selected from O and S, Q1 ^ is selected from hydroxyl and thiol. A82, A83, A84, and A8^ are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A80 and A81 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; with the provisos that A81 and A82 may bond together to form a ring structure, A82 and A83 may bond together to form a ring structure, A83 and A84 may bond together to form a ring structure, A84 and A85 may bond together to form a ring structure; or
general formula (x) is
Figure imgf000136_0002
, subscript x is an integer from 0 to 1 ,
Q1 6 is selected from N, O, P, and S, Q1 4 is selected from oxygen and sulphur, Q1 5 is selected from hydroxyl and thiol, each A7^ is independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group, A77 and A78 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A76 and A77 may bond together to form a ring structure, and A77 and A78 may bond together to form a ring structure; or
a compound of general formula (xi)
Figure imgf000136_0003
, where subscript x is an integer from 0 to 2, subscripts y and z are each independently an integer from 0 to 1 , dashed lines indicate single or double bonds, Q50 is selected from N and C, with the proviso that the two N atoms may be positively charged with a balancing negatively charged anion, A86 and each A89 are each independently selected from a monovalent organic group, hydrogen, or an inorganic heteroatom containing group, with the proviso that A86 may not contain thiol or phenyl di-isopropyl, A87 A88, A9^, and A91 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group, and with the provisos that A88 and A90 may be bonded together to form a ring structure, A87 and A88 may be bonded together to form a ring structure, A87 and A86 may be bonded together to form a ring structure, A86 and A91 may be bonded together to form a ring structure, A91 and A90 may be bonded together to form a ring structure; or
Λ 90 Λ 91
general formula (xii) is
Figure imgf000137_0001
_ subscript x is an integer from 1 to 5, Q20 is selected from N and P, dashed lines indicate a single or double bond, A90, A91 , A92,
A93 A94, and A95 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that when Q2^ is nitrogen and A9^ is hydrogen then A9^ and A91 are not cyclohexyl, and with the proviso that A90 and A91 are not be di(tert-butyl) phenol; with the provisos that
A90 and A91 may be bonded together to form a ring structure, with the proviso that when the ring is a phosphalane ring, then A92 and A98 form a phenyl group. Alternatively, A91 and A92 may be bonded together to form a ring structure, A92 and A93 may be bonded together to form a ring structure with the proviso that when Q20 is nitrogen then the ring structure is not indene, A93 and A94 may be bonded together to form a ring structure with the proviso that when Q2^ is nitrogen then there are no other hetero-atoms in the ring structure with Q20, A94 and A95 may be bonded together to form a ring structure, and with the proviso that when subscript x is 2 or more, then two or more instances of A93 may bond together to form a ring structure; or general formula (xiii) is
Figure imgf000138_0001
subscript x is an integer from 0 to 1 , Q21 is selected from N, O, P, and S, A96, A97, A98, A99, A1 00, A1 01 , A1 02
A 03, A 04, A 05, A 06, A °7, and A 08 are each independently selected from a monovalent organic group, hydrogen, a halogen, and an inorganic heteroatom containing group; with the provisos that A96 and A97 may bond together to form a ring structure, A99 and A1 00 may bond together to form a ring structure, A96 and A1 08 may bond together to form a ring structure, A108 and A107 may bond together to form a ring structure, A107 and A106 may bond together to form a ring structure, A106 and A105 may DOrid together to form a ring structure, A105 anc| A104 may Donc| together to form a ring structure, with the proviso that the bridging atom is not N in an amine group, and with the provisos that A1 °4 and A103 may Donc| together to form a ring structure, A103 anc| A102 may Donc| together to form a ring structure, A1 02 ANC| A101 may bond together to form a ring structure; or
general formula (xiv) '
Figure imgf000138_0002
, where subscripts x and y are each independently an integer from 0 to 5, and A1 1 1 , A1 1 °, and A1 1 2 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group; or
general formula (xv) is
Figure imgf000138_0003
_ where Q22 and Q23 are each independently selected from oxygen and sulphur, and A1 15, A1 16, A1 1 7, and A1 1 8 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A1 16 and A1 15 may combine to form a ring structure, A1 18 and A1 1 9 may combine to form a ring structure; or general formula (xvi) is
Figure imgf000139_0001
' subscripts x and y are each independently integers from 0 to 4, Q24 and Q25 are each independently selected from O and S, subscript z is an integer from 0 to 1 , each A1 20 is independently selected from a monovalent organic group, hydrogen, halogen, and inorganic heteroatom containing group, and A1 21 and A1 22 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; or
general formula (xvii)
Figure imgf000139_0002
is selected from O and S, Q27 is selected from N and C, subscript x is an integer from 0 to 4, A1 25, A1 26, A127, A1 28, and A1 30 are each independently selected from a monovalent organic group, hydrogen, a halogen, or an inorganic heteroatom containing group, and A1 29 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group, with the proviso that A1 28 and A1 29 may combine to form a ring structure.
16. The method of claim 15, where at least one of the following conditions is satisfied:
The ligand has general formula (ii), and the ligand is selected from the group consisting of ligands 510, 788, 799, in Table 2; or
The ligand has general formula (iii), and the ligand is selected from the group consisting of ligands 7282 and 10364 in Table 2; or
The ligand has general formula (iv), and the ligand is selected from the group consisting of ligands 755, 2915, 3472, 3746, 4098, 41 17, 6870, 7496, 10132 and in Table 2; or
The ligand has general formula (v), and the ligand is selected from the group consisting of ligands 788, 799, 1 1 16, and 1547 in Table 2; or The ligand has general formula (vi), and the ligand is selected from the group consisting of ligands 1249, 2075, 2272, 3191 , 5177, 6322, 6372, and 7534 in Table 2; or
The ligand has general formula (vii), and the ligand is selected from the group consisting of ligands 735, 1936, 2956, and 9042 in Table 2; or
The ligand has general formula (viii), and the ligand is selected from the group consisting of ligands 3746, 6322, 6372, 7534, 8881 , 9042, and 9072 in Table 2; or
The ligand has general formula (ix), and the ligand is selected from the group consisting of ligands or 3500 in Table 2; or
The ligand has general formula (x), and the ligand is selected from the group consisting of ligands 2806 in Table 2; or
The ligand has general formula (xi), and the ligand is selected from the group consisting of ligands 8538, 8881 , 9042, 10376, 10379, 10381 , 10450, 10452, and 10454 in Table 2; or
The ligand has general formula (xii), and the ligand is selected from the group consisting of ligands 10385, 10392, 10398, 10400, and 10407 in Table 2; or
The ligand has general formula (xiii), and the ligand is selected from the group consisting of ligands 10403 and 10405 in Table 2; or
The ligand has general formula (xiv), and the ligand is selected from the group consisting of ligands 3179 in Table 2; or
The ligand has general formula (xv), and the ligand is selected from the group consisting of ligands 4570 in Table 2; or
The ligand has general formula (xvi), and the ligand is selected from the group consisting of ligands 4548 in Table 2; or
The ligand has general formula (xvii), and the ligand is selected from the group consisting of 10441 and 10445 in Table 2.
17. A method comprising:
(1 ) combining ingredients comprising an Ni precursor and a ligand, thereby preparing a reaction product, where
the Ni precursor has formula (i) N1-A2, where each A is independently a monovalent organic group containing at least one silicon atom, and
the ligand is one of general formula (ii), general formula (iii), general formula (iv), general formula (v), general formula (vi), general formula (vii), general formula (viii), general formula (ix), general formula (x), general formula (xi), general formula (xii), general formula (xiii), general formula (xv), general formula (xvi), or general formula (xviii), where general formula (ii) is
Figure imgf000141_0001
, where subscript x is an integer from 0 to 1 , Q1 is selected from oxygen, sulphur, nitrogen and phosphorus, A1 , A3, A4, A5, and
A6 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A6 is not chlorobenzene, A2 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the provisos that A2 and A3 may bond together to form a ring structure; A3 and A4 may bond together to form a ring structure; A4 and A5 may bond together to form a ring structure; A5 and A6 may bond together to form a ring str
general formula (iii) is
Figure imgf000141_0002
, where Q2 is oxygen or sulphur,
A7, A3, Α^, A10, and A12 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A1 1 is selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that A1 1 is not benzyl, and with the provisos that A7 and A3 may combine to form a ring structure; A3 and A^ may combine to form a ring structure; A 9 and A1 ^ may combine to form a ring structure; and A1 1 and A1 2 may combine to form a ring structure; or, general formula (iv) is
Figure imgf000142_0001
, subscript x is an integer from 0 to 1 , Q3 is selected from oxygen, sulphur, and nitrogen, A1 5, A1 6, A1 7, A1 8, A20, and A21 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, each A1 9 is independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that A1 9 does not contain diphenylphosphine, A20 and
A21 can be bonded together to form a ring structure; with the provisos that A1 9 and A1 8 can be bonded together to form a ring structure, A1 8 and A1 7 can be bonded together to form a ring structure, A1 7 and A1 6 can be bonded together to form a ring structure, A1 6 and A1 5 can be bonded together to form a ring structure; or,
general formula (v) is
Figure imgf000142_0002
, where subscript x is an integer from 0 to 1 , dashed lines denote either a single or double bond, subscript y is an integer from 0 to 1 , Q4 and Q5 are each independently selected from N, O, P, and S, A25, A26, A27, A28, A29, A30, A81 , and A82 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group; with the provisos that A29 and A25 may be bonded together to form a ring structure, A25 and A26 may be bonded together to form a ring structure, A26 and A27 may be bonded together to form a ring structure, A27 and A28 may be bonded together to form a ring structure, and A28 and A82 may be bonded together to form a ring structure, A29 and A80 may be bonded together to form a ring structure, with the proviso that the ring structure formed by bonding together A29 and A8^ is not pyrrole and A81 and A82 may be bonded together to form a ring structure, with the proviso that the ring structure formed by bonding together A81 and A82 jS not pyrrol
general formula (vi) is
Figure imgf000143_0001
, where subscript x is an integer from 0 to 1 , Q8 is selected from N, O, P, and S, A45, A46, A47, A49, A50, A51 , and A52 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, with the proviso that when Q8 is sulphur then A45 is not benzene, A48 is selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; with the provisos that A45 and A52 may combine to form a ring structure, A^2 and A^1 may combine to form a ring structure, A^1 and A^O may combine to form a ring structure, A^O and A49 may combine to form a ring structure, A45 and A4^ may combine to form a ring structure; or,
general f
Figure imgf000143_0002
, where subscript x is an integer from 0 to 1 , a dashed line indicates a single or double bond, A56 and A57 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A58 and A55 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A56 and A^7 may combine to form a ring structure, and A^5 and A^6 may combine to form a ring structure; or
general formula (viii) is
Figure imgf000144_0001
, subscript x is an integer from 0 to 1 , subscript y is an integer from 0 to 1 , Q1 1 and Q1 2 are each independently selected from N, O, P, and S, with the proviso that if Q1 1 or Q1 2 are nitrogen then they are not imine nitrogen, dashed lines represent either single or double bonds, A^O, A^1 , /\β5, and A66 are each independently selected from a monovalent organic group, hydrogen, a halogen atom , and an inorganic heteroatom containing group, each A62, each A63, and each A64 are independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group; with the provisos that A60 and A61 may be bonded together to form a ring structure, A61 and A62 may be bonded together to form a ring structure, A62 and A63 may be bonded together to form a ring structure, A63 and A64 may be bonded together to form a ring structure, A64 and A65 may be bonded together to form a ring structure, A65 and A66 may be bonded together to form a ring structure, A63 and A61 may be bonded together to form a ring structure; or,
general formula (ix) is
Figure imgf000144_0002
, subscript x is an integer from 0 to 1 , Q1 7 is selected from N, O, P, and S, and C, with the proviso that when Q17 is C, the carbon forms a carbonyl bond with A31 and a hydroxyl group with A30 , Q18 is selected from O and S, Q1 ^ is selected from hydroxyl and thiol. A32, A33, A34, and A3^ are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group, A30 and A31 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; with the provisos that A31 and A32 may bond together to form a ring structure, A32 and A33 may bond together to form a ring structure, A33 and A34 may bond together to form a ring structure, A34 and A35 may bond together to form a ring structure; or general formula (x) is
Figure imgf000145_0001
, subscript x is an integer from 0 to 1 ,
Q1 6 is selected from N, O, P, and S, Q1 4 is selected from oxygen and sulphur, Q1 5 is selected from hydroxyl and thiol, each A7^ js independently selected from a monovalent organic group, hydrogen, halogen atom, and an inorganic heteroatom containing group, A77 and A78 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A76 and A77 may bond together to form a ring structure, and A77 and A78 may bond together to form a ring structure; or
a compound of general formula (xi)
Figure imgf000145_0002
, where subscript x is an integer from 0 to 2, subscripts y and z are each independently an integer from 0 to 1 , dashed lines indicate single or double bonds, Q50 is selected from N and C, with the proviso that the two N atoms may be positively charged with a balancing negatively charged anion, A86 and each A89 are each independently selected from a monovalent organic group, hydrogen, or an inorganic heteroatom containing group, with the proviso that A86 may not contain thiol or phenyl di-isopropyl, A87 A88, A9^, and A91 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group, and with the provisos that A88 and A90 may be bonded together to form a ring structure, A87 and A88 may be bonded together to form a ring structure, A87 and A86 may be bonded together to form a ring structure, A86 and A91 may be bonded together to form a ring structure, A91 and A90 may be bonded together to form a ring structure; or
general formula (xii) is
Figure imgf000145_0003
_ subscript x is an integer from 1 to 5, Q20 is selected from N and P, dashed lines indicate a single or double bond, A9^, A91 , A92, A98 A94, and A95 are each independently selected from a monovalent organic group, hydrogen, a halogen atom, and an inorganic heteroatom containing group with the proviso that when Q20 is nitrogen and A9^ js hydrogen then A90 and A91 are not cyclohexyl, and with the proviso that A90 and A91 are not be di(tert-butyl) phenol; with the provisos that
A90 and A91 may be bonded together to form a ring structure, with the proviso that when the ring is a phosphalane ring, then A92 and A93 form a phenyl group. Alternatively, A91 and A92 may be bonded together to form a ring structure, A92 and A93 may be bonded together to form a ring structure with the proviso that when Q20 is nitrogen then the ring structure is not indene, A93 and A94 may be bonded together to form a ring structure with the proviso that when Q20 is nitrogen then there are no other hetero-atoms in the ring structure with Q20, A94 and A95 may be bonded together to form a ring structure, and with the proviso that when subscript x is 2 or more, then two or more instances of A93 may bond together to form a ring structure; or,
general formula (xiii) is
Figure imgf000146_0001
, subscript x is an integer from
0 to 1 , Q21 is selected from N, O, P, and S, A96, A97, A98, A99, A1 00, A1 01 , A1 02, A1 03, A104, A1 05J A1 06, A1 07, and A1 08 are each independently selected from a monovalent organic group, hydrogen, a halogen, and an inorganic heteroatom containing group; with the provisos that A9^ and A97 may bond together to form a ring structure, A99 and A1 00 may bond together to form a ring structure, A96 and A1 °8 may Donc| together to form a ring structure, A1 08 and A1 07 may bond together to form a ring structure, A1 07 and A1 06 may bond together to form a ring structure, A1 °6 ANC| A1 05 may Donc| together to form a ring structure, A1 °5 ANC| A1 04 may Donc| together to form a ring structure, with the proviso that the bridging atom is not N in an amine group, and with the provisos that A1 04 ANC| A1 03 may bond together to form a ring structure, A1 03 and A1 02 may bond together to form a ring structure, A1 02 and A1 °1 may bond together to form a ring structure; or, ^1 18 ^1 17 ^1 16
general formula (xv) is Q Q _ where Q22 and Q23 are each independently selected from oxygen and sulphur, and A1 15, A1 16, A1 1 7, and A1 1 3 are each independently selected from a monovalent organic group, hydrogen, or an inorganic group; with the provisos that A1 16 and A1 15 may combine to form a ring structure, A1 1 3 and A1 19 may combine to form a ring structure; or
general formula (xvi) is
Figure imgf000147_0001
, subscripts x and y are each independently integers from 0 to 4, Q24 and Q25 are each independently selected from O and S, subscript z is an integer from 0 to 1 , each A1 20 is independently selected from a monovalent organic group, hydrogen, halogen, and inorganic heteroatom containing group, and A1 21 and A1 22 are each independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group; or
general formula (xviii) is
Figure imgf000147_0002
, where A132, A133, and A 34 are each independently selected from a monovalent organic group, hydrogen, a halogen, or an inorganic heteroatom containing group, and A1 31 and A1 35 are independently selected from a monovalent organic group, hydrogen, and an inorganic heteroatom containing group.
18. The method of claim 17, where at least one of the following conditions is satisfied:
The ligand has general formula (ii), and the ligand is selected from the group consisting of 483, 486, 488, 512, 777, 785, 6269, and 8842 in Table 2; or
The ligand has general formula (iii), and the ligand is selected from the group consisting of 7377 in Table 2; or The ligand has general formula (iv), and the ligand is selected from the group consisting of 2072, 3586, and 7124 in Table 2; or
The ligand has general formula (v), and the ligand is selected from the group consisting of 165, 1 125, 1214, 3547, 4151 , 4202, 7639, and 8749 in Table 2; or
The ligand has general formula (vi), and the ligand is selected from the group consisting of 635, 1888, 2061 , 2062, 4202, 4990, 6253, 6340, and 7124 in Table 2; or
The ligand has general formula (vii), and the ligand is selected from the group consisting of 2956 and 10267 in Table 2; or
The ligand has general formula (viii), and the ligand is selected from the group consisting of 1214, or 1769, 3499, 3547, 3749, and 8977 in Table 2; or
The ligand has general formula (ix), and the ligand is selected from the group consisting of 2816 and 3505 in Table 2; or
The ligand has general formula (x), and the ligand is selected from the group consisting of 2363 and 4226 in Table 2; or
The ligand has general formula (xi), and the ligand is selected from the group consisting of 4226, 6253, 8500, 8749, 8977, 10380, 10390, 10451 , 10455, and 10457 in Table 2; or
The ligand has general formula (xii), and the ligand is selected from the group consisting of 10384, 10386, 10391 , and 10399 in Table 2; or
The ligand has general formula (xiii), and the ligand is selected from the group consisting of 10406 and 10446 in Table 2; or
The ligand has general formula (xv), and the ligand is selected from the group consisting of 8768, in Table 2; or
The ligand has general formula (xvi), and the ligand is selected from the group consisting of 6510 in Table 2; or
The ligand has general formula (xviii), and the ligand is selected from the group consisting of 10453 in Table 2.
19. The method of one of claims 15 - 18, further comprising (2) combining the reaction product with a reducing agent. (NaEt3BH)
20. The method of any one of claims 1 -19, where the reaction product comprises a Ni- ligand complex and a by-product of reaction of the Ni precursor and the ligand or of a side reaction therein.
21. The method of claim 20, further comprising removing all or a portion of the by-product.
22. The method of any one of claims 1 -21 , further comprising using the product prepared by the method as a hydrosilylation catalyst. 23. A composition comprising:
(A) a product prepared by the method of any one of claims 1 - 9; and
(B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction; and
(c) a polyorganohydrogensiloxane.
24. A composition comprising:
(A) a product prepared by the method of any one of claims 10 - 19;
(B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction; and
(C) a silane of formula R4 eSiHf, where subscript e is 0, 1 , 2, or 3; subscript f is 1 , 2, 3, or 4, with the proviso that a sum of (e + f) is 4, and each R4 is independently a halogen atom or a monovalent organic group.
25. The composition of claim 21 or claim 22, where the composition further comprises one or more additional ingredients, which are distinct from ingredients (A), (B), and (C), and which are selected from the group consisting of (D) a spacer; (E) an extender, a plasticizer, or a combination thereof; (F) a filler; (G) a filler treating agent; (H) a biocide; (I) a stabilizer, (J) a flame retardant; (K) a surface modifier; (L) a chain lengthener; (M) an endblocker; (N) a flux agent; (O) an anti-aging additive; (P) a pigment; (Q) an acid acceptor; (R) a rheological additive; (S) a vehicle; (T) a surfactant; (U) a corrosion inhibitor; and a combination thereof. 26. A method for making the composition of any one of claims 23-25, comprising:
mixing ingredients comprising ingredients (A), (B), and (C); or
mixing ingredients comprising ingredients (A) and (B), and optionally one or more of (D), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O), (P), (Q), (R), (S), (T), and (U) to form a curing agent and mixing ingredients comprising ingredients (B), and (C) and optionally one
147 or more of (D), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O), (P), (Q), (R), (S), (T), and (U) to form a base, and mixing the curing agent and the base;
so as to make the composition. 27. A reaction product of the composition of any one of claims 23-25.
148
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016014005A (en) * 2014-06-12 2016-01-28 国立研究開発法人産業技術総合研究所 Method for producing organosilicon compound and catalyst composition
JP2016520083A (en) * 2013-05-15 2016-07-11 モメンティブ パフォーマンス マテリアルズ インコーポレイテッド Activation of metal salts with silylhydrides and their use in hydrosilylation reactions.
KR20170042319A (en) 2014-08-12 2017-04-18 고쿠리쓰다이가쿠호진 규슈다이가쿠 Hydrosilylation reaction catalyst
KR20170042681A (en) 2014-08-19 2017-04-19 고쿠리쓰다이가쿠호진 규슈다이가쿠 Hydrosilylation iron catalyst
US9708355B2 (en) 2013-06-12 2017-07-18 Arizona Board Of Regents On Behalf Of Arizona State University First-row transition metal hydrogenation and hydrosilylation catalysts
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US10000515B2 (en) 2014-08-12 2018-06-19 Kyushu University, National University Corporation Hydrosilylation reaction catalyst
WO2018159595A1 (en) 2017-02-28 2018-09-07 国立大学法人九州大学 Catalyst for hydrosilylation reaction, hydrogenation reaction, and hydrosilane reduction reaction
KR20180108656A (en) 2016-01-22 2018-10-04 신에쓰 가가꾸 고교 가부시끼가이샤 The novel isocyanide compound and the hydrosilylation reaction catalyst

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10058542B1 (en) 2014-09-12 2018-08-28 Thioredoxin Systems Ab Composition comprising selenazol or thiazolone derivatives and silver and method of treatment therewith
WO2016099727A2 (en) * 2014-12-19 2016-06-23 Dow Corning Corporation Ligand components, associated reaction products, activated reaction products, hydrosilylation catalysts and hydrosilylation curable compositions including the ligand components, and associated methods for preparing same
CN106881131B (en) * 2015-12-15 2019-11-12 中国科学院大连化学物理研究所 A kind of supported non-precious metal catalyst and its preparation and the application in nitrile synthesis
CN113244963B (en) * 2021-05-17 2022-05-27 杭州师范大学 Polyethylene glycol N, P coordination non-noble metal catalyst, preparation thereof and application thereof in olefin catalytic hydrosilylation reaction

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2676182A (en) 1950-09-13 1954-04-20 Dow Corning Copolymeric siloxanes and methods of preparing them
US3159601A (en) 1962-07-02 1964-12-01 Gen Electric Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes
US3220972A (en) 1962-07-02 1965-11-30 Gen Electric Organosilicon process using a chloroplatinic acid reaction product as the catalyst
US3296291A (en) 1962-07-02 1967-01-03 Gen Electric Reaction of silanes with unsaturated olefinic compounds
US3419593A (en) 1965-05-17 1968-12-31 Dow Corning Catalysts for the reaction of = sih with organic compounds containing aliphatic unsaturation
US3516946A (en) 1967-09-29 1970-06-23 Gen Electric Platinum catalyst composition for hydrosilation reactions
US3814730A (en) 1970-08-06 1974-06-04 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
US3989668A (en) 1975-07-14 1976-11-02 Dow Corning Corporation Method of making a silicone elastomer and the elastomer prepared thereby
US4370358A (en) 1980-09-22 1983-01-25 General Electric Company Ultraviolet curable silicone adhesives
US4584355A (en) 1984-10-29 1986-04-22 Dow Corning Corporation Silicone pressure-sensitive adhesive process and product with improved lap-shear stability-I
US4585836A (en) 1984-10-29 1986-04-29 Dow Corning Corporation Silicone pressure-sensitive adhesive process and product with improved lap-shear stability-II
US4591622A (en) 1984-10-29 1986-05-27 Dow Corning Corporation Silicone pressure-sensitive adhesive process and product thereof
US4707531A (en) 1985-02-22 1987-11-17 Toray Silicone Co., Ltd. Method for producing organosilicon polymers and the polymers prepared thereby
US4766176A (en) 1987-07-20 1988-08-23 Dow Corning Corporation Storage stable heat curable organosiloxane compositions containing microencapsulated platinum-containing catalysts
US4784879A (en) 1987-07-20 1988-11-15 Dow Corning Corporation Method for preparing a microencapsulated compound of a platinum group metal
US5017654A (en) 1988-06-30 1991-05-21 Toray Silicone Company, Limited Thermosetting organosiloxane composition
US5036117A (en) 1989-11-03 1991-07-30 Dow Corning Corporation Heat-curable silicone compositions having improved bath life
US5175325A (en) 1991-02-14 1992-12-29 Dow Corning Limited Platinum complexes and use thereof
EP0347895B1 (en) 1988-06-23 1993-11-18 Toray Silicone Company, Limited Method for preparing a particulate material comprising a platinum-containing hydrosilylation catalyst and a silicone resin.
US5310843A (en) 1991-10-17 1994-05-10 Dow Corning Toray Silicone Co., Ltd. Organopolysiloxane and method for the preparation thereof
WO2003093369A1 (en) 2002-05-01 2003-11-13 Dow Corning Corporation Compositions having improved bath life
WO2003093349A1 (en) 2002-05-01 2003-11-13 Dow Corning Corporation Organohydrogensilicon compounds

Family Cites Families (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL129346C (en) 1966-06-23
JPS4925649B1 (en) * 1970-03-13 1974-07-02
US3989667A (en) 1974-12-02 1976-11-02 Dow Corning Corporation Olefinic siloxanes as platinum inhibitors
US4087585A (en) 1977-05-23 1978-05-02 Dow Corning Corporation Self-adhering silicone compositions and preparations thereof
US4284751A (en) 1980-05-14 1981-08-18 Products Research & Chemical Corp. Polyurethane sealant system
US4550152A (en) * 1983-10-28 1985-10-29 General Electric Company Nickel complex catalyst for hydrosilation reactions
JP2512468B2 (en) 1987-04-13 1996-07-03 鐘淵化学工業株式会社 Curable resin composition
US5580925A (en) 1989-02-28 1996-12-03 Kanegafuchi Chemical Industry, Co., Ltd. Curable organic polymers containing hydrosilyl groups
US5063267A (en) 1990-11-28 1991-11-05 Dow Corning Corporation Hydrogen silsesquioxane resin fractions and their use as coating materials
JP3029680B2 (en) 1991-01-29 2000-04-04 東レ・ダウコーニング・シリコーン株式会社 Organopentasiloxane and method for producing the same
CA2139356C (en) 1992-07-01 2001-02-06 Donna J. Crowther Transition metal olefin polymerization catalysts
US5248715A (en) 1992-07-30 1993-09-28 Dow Corning Corporation Self-adhering silicone rubber with low compression set
CN100357327C (en) * 1995-01-24 2007-12-26 纳幕尔杜邦公司 'Alpha'-olefines and olefin polymers and processes therefor
US5683527A (en) 1996-12-30 1997-11-04 Dow Corning Corporation Foamable organosiloxane compositions curable to silicone foams having improved adhesion
US6034240A (en) 1998-03-09 2000-03-07 Symyx Technologies, Inc. Substituted aminomethylphosphines, coordination complexes of aminomethylphosphines and their synthesis
US6350916B1 (en) 1998-04-17 2002-02-26 Symyx Technologies, Inc. Selective oxidation of alcohols to aldehydes or ketones
JP3444199B2 (en) 1998-06-17 2003-09-08 信越化学工業株式会社 Thermal conductive silicone rubber composition and method for producing the same
US6974878B2 (en) 2001-03-21 2005-12-13 Symyx Technologies, Inc. Catalyst ligands, catalytic metal complexes and processes using same
US6521793B1 (en) 1998-10-08 2003-02-18 Symyx Technologies, Inc. Catalyst ligands, catalytic metal complexes and processes using same
US20020010291A1 (en) 1998-12-04 2002-01-24 Vince Murphy Ionic liquids and processes for production of high molecular weight polyisoolefins
WO2000032572A2 (en) 1998-12-04 2000-06-08 Symyx Technologies Combinatorial discovery and testing of ionic liquids
JP2000169513A (en) * 1998-12-09 2000-06-20 Mitsui Chemicals Inc Olefin polymerization catalyst and process
US6177519B1 (en) 1999-03-02 2001-01-23 Exxon Chemical Patents, Inc. Silane grafted copolymers of an isomonoolefin and a vinyl aromatic monomer
US6197714B1 (en) * 1999-03-23 2001-03-06 Cryovac, Inc. Supported catalysts and olefin polymerization processes utilizing same
AU4186500A (en) 1999-04-01 2000-10-23 Symyx Technologies, Inc. Polymerization catalyst ligands, catalytic metal complexes and compositions and processes using and methods of making same
EP1131283A1 (en) 1999-09-10 2001-09-12 Symyx Technologies Catalyst ligands, catalytic metal complexes and processes using and methods of making same
US6177585B1 (en) 2000-05-19 2001-01-23 Dow Corning Corporation Bimetallic platinum catalysts for hydrosilations
US7078164B1 (en) 2000-06-19 2006-07-18 Symyx Technologies, Inc. High throughput screen for identifying polymerization catalysts from potential catalysts
US6790298B2 (en) 2000-07-10 2004-09-14 Tini Alloy Company Method of fabrication of free standing shape memory alloy thin film
CN1184243C (en) * 2000-09-14 2005-01-12 中国科学院化学研究所 Process for preparing long-chain branched polyethylene elastomer
WO2003010207A1 (en) 2001-07-23 2003-02-06 Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences Catalyst for polymerization or copolymerization of olefins, preparation and use of the same
KR20040097265A (en) * 2002-04-04 2004-11-17 데구사 아게 Bisphosphines as bidentate ligands
DE10257938A1 (en) 2002-12-12 2004-06-24 Oxeno Olefinchemie Gmbh Production of complexes of Group 6-10 elements, useful for hydroformylation, hydrogenation, coupling and polymerization reactions, involves reaction of Group 6-10 metal with unsaturated nitrogen containing compounds
GB0305927D0 (en) 2003-03-14 2003-04-23 Ic Innovations Ltd Compound
GB0306430D0 (en) 2003-03-20 2003-04-23 Bp Chem Int Ltd Polymerisation and oligomerisation catalysts
WO2005058917A2 (en) * 2003-12-17 2005-06-30 The Penn State Research Foundation New oxazoline ligands for asymmetric catalysis
CA2554006A1 (en) * 2004-02-26 2005-09-09 Universiteit Gent Metal complexes for use in olefin metathesis and atom group transfer reactions
DE602005019988D1 (en) 2004-03-17 2010-04-29 Dow Global Technologies Inc CATALYST COMPOSITION WITH SHUTTERING AGENT FOR THE PRODUCTION OF ETHYLENE MULTIBLOCK COPOLYMER
CN1260233C (en) * 2004-04-02 2006-06-21 中国科学院上海有机化学研究所 Chirality phosphine ligand, synthesis, and application in asymmetric catalyfic reaction
JP2005306994A (en) 2004-04-21 2005-11-04 Shin Etsu Chem Co Ltd Silicone emulsion composition for forming coating film
GB0410749D0 (en) 2004-05-14 2004-06-16 Dow Corning Ireland Ltd Coating apparatus
CN100537018C (en) 2004-06-16 2009-09-09 陶氏环球技术公司 Apparatus and method for Ziegler-Natta research
CN1315573C (en) * 2005-01-07 2007-05-16 吉林大学 Beta-diimide nickel compound/alkyl aluminium catalyst system and its application
WO2006119311A2 (en) 2005-05-02 2006-11-09 Symyx Technologies, Inc. High surface area metal and metal oxide materials and methods of making same
TWI426089B (en) 2005-09-15 2014-02-11 Dow Global Technologies Llc Catalytic olefin block copolymers with controlled block sequence distribution
US20080300358A1 (en) 2005-12-08 2008-12-04 Leon Neal Cook Continuous Process For Production Of Silicone Pressure Sensitive Adhesives
CN100344656C (en) * 2006-05-11 2007-10-24 复旦大学 Process for preparation of polynorbornene
CN100395268C (en) * 2006-05-11 2008-06-18 复旦大学 N-N double teeth ligand, three-coordination monovalence nickel olefin polymerization catalyst, and its prepn. method
RU2448127C2 (en) 2006-07-03 2012-04-20 Дау Корнинг Корпорейшн Chemically curable all-in-one warm edge spacer and seal
JP2010506034A (en) 2006-10-10 2010-02-25 ダウ・コーニング・コーポレイション Bulking agents for organosiloxane compositions
EP1925623A1 (en) 2006-11-24 2008-05-28 Total Petrochemicals Research Feluy Polymerisation of ethylene and alpha-olefins with pyrrol-iminophenol complexes.
JP5349806B2 (en) * 2007-01-30 2013-11-20 三洋化成工業株式会社 Urethane resin composition
GB0708347D0 (en) 2007-05-01 2007-06-06 Dow Corning Polymer compositions
GB0724914D0 (en) 2007-12-21 2008-01-30 Dow Corning Moisture curable compositions
WO2009095898A1 (en) * 2008-02-01 2009-08-06 L'air Liquide-Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude New metal precursors containing beta-diketiminato ligands
JP5647153B2 (en) * 2009-02-06 2014-12-24 ダウ グローバル テクノロジーズ エルエルシー Method for producing alkylaluminum
CN102341459B (en) 2009-03-12 2014-01-01 道康宁公司 Thermal interface materials and methods for their preparation and use
US20120009366A1 (en) 2009-03-23 2012-01-12 Galbraith Thomas W Chemically Curing All-In-One Warm Edge Spacer And Seal
US8236915B2 (en) * 2009-07-10 2012-08-07 Momentive Performance Materials Inc. Hydrosilylation catalysts
CN101613425B (en) * 2009-07-21 2011-05-04 浙江大学 Catalyst of polyethylene with double peak and/or broad peak molecular weight distribution
CN101787045B (en) * 2010-02-08 2012-10-03 浙江大学 Method for catalyzing hydrosilylation with ruthenium compound
KR101890606B1 (en) * 2010-11-24 2018-09-28 모멘티브 퍼포먼스 머티리얼즈 인크. In-situ activation of metal complexes used as hydrosilylation catalysts
BR112013012734A2 (en) 2010-11-24 2016-09-13 Univ Cornell Selective non-precious metal catalyzed monohydrosilylation of polyunsaturated compounds
CN102179266B (en) * 2011-03-18 2012-11-28 杭州师范大学 Supported catalyst for hydrosilylation and preparation method thereof
US9993812B2 (en) 2012-04-17 2018-06-12 Momentive Pereformance Materials Inc. High activity catalyst for hydrosilylation reactions and methods of making the same

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2676182A (en) 1950-09-13 1954-04-20 Dow Corning Copolymeric siloxanes and methods of preparing them
US3159601A (en) 1962-07-02 1964-12-01 Gen Electric Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes
US3220972A (en) 1962-07-02 1965-11-30 Gen Electric Organosilicon process using a chloroplatinic acid reaction product as the catalyst
US3296291A (en) 1962-07-02 1967-01-03 Gen Electric Reaction of silanes with unsaturated olefinic compounds
US3419593A (en) 1965-05-17 1968-12-31 Dow Corning Catalysts for the reaction of = sih with organic compounds containing aliphatic unsaturation
US3516946A (en) 1967-09-29 1970-06-23 Gen Electric Platinum catalyst composition for hydrosilation reactions
US3814730A (en) 1970-08-06 1974-06-04 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
US3989668A (en) 1975-07-14 1976-11-02 Dow Corning Corporation Method of making a silicone elastomer and the elastomer prepared thereby
US4370358A (en) 1980-09-22 1983-01-25 General Electric Company Ultraviolet curable silicone adhesives
US4585836A (en) 1984-10-29 1986-04-29 Dow Corning Corporation Silicone pressure-sensitive adhesive process and product with improved lap-shear stability-II
US4584355A (en) 1984-10-29 1986-04-22 Dow Corning Corporation Silicone pressure-sensitive adhesive process and product with improved lap-shear stability-I
US4591622A (en) 1984-10-29 1986-05-27 Dow Corning Corporation Silicone pressure-sensitive adhesive process and product thereof
US4707531A (en) 1985-02-22 1987-11-17 Toray Silicone Co., Ltd. Method for producing organosilicon polymers and the polymers prepared thereby
US4766176A (en) 1987-07-20 1988-08-23 Dow Corning Corporation Storage stable heat curable organosiloxane compositions containing microencapsulated platinum-containing catalysts
US4784879A (en) 1987-07-20 1988-11-15 Dow Corning Corporation Method for preparing a microencapsulated compound of a platinum group metal
EP0347895B1 (en) 1988-06-23 1993-11-18 Toray Silicone Company, Limited Method for preparing a particulate material comprising a platinum-containing hydrosilylation catalyst and a silicone resin.
US5017654A (en) 1988-06-30 1991-05-21 Toray Silicone Company, Limited Thermosetting organosiloxane composition
US5036117A (en) 1989-11-03 1991-07-30 Dow Corning Corporation Heat-curable silicone compositions having improved bath life
US5175325A (en) 1991-02-14 1992-12-29 Dow Corning Limited Platinum complexes and use thereof
US5310843A (en) 1991-10-17 1994-05-10 Dow Corning Toray Silicone Co., Ltd. Organopolysiloxane and method for the preparation thereof
WO2003093369A1 (en) 2002-05-01 2003-11-13 Dow Corning Corporation Compositions having improved bath life
WO2003093349A1 (en) 2002-05-01 2003-11-13 Dow Corning Corporation Organohydrogensilicon compounds

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016520083A (en) * 2013-05-15 2016-07-11 モメンティブ パフォーマンス マテリアルズ インコーポレイテッド Activation of metal salts with silylhydrides and their use in hydrosilylation reactions.
US9708355B2 (en) 2013-06-12 2017-07-18 Arizona Board Of Regents On Behalf Of Arizona State University First-row transition metal hydrogenation and hydrosilylation catalysts
US10407451B2 (en) 2013-06-12 2019-09-10 Arizona Board Of Regents On Behalf Of Arizona State University First-row transition metal hydrogenation and hydrosilylation catalysts
JP2016014005A (en) * 2014-06-12 2016-01-28 国立研究開発法人産業技術総合研究所 Method for producing organosilicon compound and catalyst composition
US10005797B2 (en) 2014-08-12 2018-06-26 Kyushu University, National University Corporation Hydrosilylation reaction catalyst
KR20170042319A (en) 2014-08-12 2017-04-18 고쿠리쓰다이가쿠호진 규슈다이가쿠 Hydrosilylation reaction catalyst
US10000515B2 (en) 2014-08-12 2018-06-19 Kyushu University, National University Corporation Hydrosilylation reaction catalyst
KR20170042681A (en) 2014-08-19 2017-04-19 고쿠리쓰다이가쿠호진 규슈다이가쿠 Hydrosilylation iron catalyst
US10239896B2 (en) 2014-08-19 2019-03-26 Kyushu University, National University Corporation Hydrosilylation iron catalyst
KR20180030080A (en) 2015-07-14 2018-03-21 고쿠리쓰다이가쿠호진 규슈다이가쿠 Hydrosilylation reaction catalyst
KR20180108656A (en) 2016-01-22 2018-10-04 신에쓰 가가꾸 고교 가부시끼가이샤 The novel isocyanide compound and the hydrosilylation reaction catalyst
US10829504B2 (en) 2016-01-22 2020-11-10 Shin-Etsu Chemical Co., Ltd. Isocyanide compound and hydrosilylation reaction catalyst
WO2018159595A1 (en) 2017-02-28 2018-09-07 国立大学法人九州大学 Catalyst for hydrosilylation reaction, hydrogenation reaction, and hydrosilane reduction reaction
KR20190125374A (en) 2017-02-28 2019-11-06 고쿠리쓰다이가쿠호진 규슈다이가쿠 Catalysts for Hydrosilylation, Hydrogenation and Hydrosilane Reduction

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US9545624B2 (en) 2017-01-17
CN103814040B (en) 2016-08-31
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JP6101695B2 (en) 2017-03-22
US20140183398A1 (en) 2014-07-03
JP2014528940A (en) 2014-10-30

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