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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
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  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0803—Compounds with Si-C or Si-Si linkages
  • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
  • C07F7/0827—Syntheses with formation of a Si-C bond
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
  • C07F7/0838—Compounds with one or more Si-O-Si sequences
  • C07F7/0872—Preparation and treatment thereof
  • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
  • C07F7/0878—Si-C bond
  • C07F7/0879—Hydrosilylation reactions
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
  • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
  • C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
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  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
  • C07F9/576—Six-membered rings
  • C07F9/58—Pyridine rings
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  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
  • B01J2231/32—Addition reactions to C=C or C-C triple bonds
  • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
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  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
  • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
  • B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
  • B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
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  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/842—Iron
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  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/845—Cobalt

Definitions

• the present invention generally relates to iigand components, activated reaction products formed from these iigand components, and the subsequent use of these activated reaction products as hydrosi!y!ation catalysts in hydrosi!y!ation curable compositions.
• the present invention also generally relates to the associated methods for preparing these activated reaction products and hydrosily!ation curable compositions.
• hydrosilyiation catalysts for catalyzing hydrosilyiation reaction are known in the art and are commercially available.
• Such conventional hydrosilyiation catalysts can be a metal selected from platinum, rhodium, ruthenium, palladium, osmium, and iridium.
• the hydrosilyiation catalyst may be a compound of such a metal, for example, chioropiatinic acid, chioropiatinic acid hexahydrate, platinum dichloride, and complexes of said compounds with low molecular weight organopoiysiloxanes or platinum compounds microencapsulated in a matrix or core/shell type structure.
• Complexes of platinum with low molecular weight organopoiysiloxanes include 1 ,3-dietheny!-1 ,1 ,3,3-tetramethy!disi!oxane complexes with platinum. These complexes may be microencapsulated in a resin matrix.
• Exemplary hydrosilyiation 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 hydrosilyiation catalysts and methods of preparing them are known in the art, as exemplified in U.S. Patents 4,766,176 and 5,017,654.
• a !igand component, and methods for preparation of the iigand component is disclosed.
• the metal precursor is according to formula (2): [M-A x ] n ,wherein M is a metal selected from iron, cobalt, manganese, nickel, and ruthertium;wherein each A is independently a displaceable substituent; wherein subscript x is an integer with a value ranging from 1 to a maximum valence number of M; and wherein n is 1 or 2.
• an activated reaction product comprises the reaction product combined with an ionic activator or a reducing agent.
• the activated reaction product is useful asa hydrosiiylation catalyst and provides advantages over previous hydrosiiylation catalysts as described above in terms of material costs and ease of preparation.
• the present invention also discloses compositionsthat utilize the activated reaction product.
• compositions comprising the activated reaction product (A); (B) a compoundhaving an average, per molecule, of one or more aiiphatica!iy unsaturated organic groups; and optionally (C) an Si-H functional compound having an average, per molecule, of at least one silicon-bonded hydrogen atom, wherein component (C) is present when component (B) does not a silicon-bonded hydrogen atom.
• 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 aikyi group, an aryl group, or an aralkyi group includes the member aikyl individually; the subgroup alkyl and aryl; and any other individual member and subgroup subsumed therein.
• Alkyl means an acyclic, branched or unbranched, saturated monovalent hydrocarbon group.
• Alkyl is exemplified by, but not limited to, methyl, ethyl, propyl (e.g., iso- propyi and/or n-propy!), butyl (e.g., isobutyl, n-butyl, tert-butyl, and/or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and/or tert-pentyl), hexyl, heptyl, octyl, nonyi, and decyl, as well as branched saturated monovalent hydrocarbon groups of 6 or more carbon atoms.
• Alkylene means a bivalent saturated aliphatic group as derived from an alkene by opening of the double bond or from an alkane by removal of two hydrogen atoms from different carbon atoms.
• the aikylene may be substituted or unsubstituted.
• Aryl means a cyclic, fully unsaturated, hydrocarbon group.
• Aryl is exemplified by, but not limited to, cyclopentadienyl, phenyl, anthracenyl, and rtaphthy!.
• Monocyclic aryl groups may have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms.
• Poiycyciic aryl groups may have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, and alternatively 12 to 14 carbon atoms.
• Arylene means a bivalent aryl group derived from an aromatic hydrocarbon by removal of a hydrogen atom from each of two carbon atoms of the nucleus.
• the arylene group has two free valences, each of which is at a carbon atom, which may be the same or different.
• Aralkyi means an alkyl group having a pendant and/or terminal aryl group or an aryl group having a pendant aikyi group.
• exemplary aralkyi groups include tolyi, xylyl, benzyl, phenylethy!, phenyl propyl, and phenyl butyl.
• the pendent or terminal aryl group or aikyl groups may be substituted or unsubstituted.
• Carbocycle and “carbocyclic” each mean a hydrocarbon ring.
• Carbocycles may be monocyclic or alternatively may be fused, bridged, or spiro poiycyciic rings.
• Monocyclic carbocycles may have 3 to 9 carbon atoms, alternatively 4 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms.
• Poiycyciic carbocycles may have 7 to 17 carbon atoms, alternatively 7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms, Carbocycles maybe saturated or partially unsaturated.
• Cycioalkyl means saturated carbocycle.
• Monocyclic cycioalkyl groups are exemplified by cyclobutyi, cyclopentyl, and eyciohexyi. Cycioalkyl groups may be substituted or unsubstituted,
• Haiogenated hydrocarbon means a hydrocarbon where one or more hydrogen atoms bonded to a carbon atom have been formally replaced with a halogen atom.
• Haiogenated hydrocarbon groups include haloalkyl groups, haiogenated carbocyclic groups, and haloaikenyl groups.
• Haloalkyl groups include fluorinated aikyl groups such as trifiuoromethyl (CF3), fiuoromethyl, trif!uoroethyl, 2-fluoropropyl, 3,3,3-trif!uoropropyi, 4,4,4- trifluorobuty!, 4,4,4,3,3-pentafiuorobutyl, 5, 5,5,4,4, 3,3-heptaf!uoropentyl, 6,6,6,5,5,4,4,3,3- nonafluorohexyl, and 8,8,8,7,7-pentafiuorooctyl; and chlorinated alkyi groups such as chloromethyl and 3-chloropropyi.
• fluorinated aikyl groups such as trifiuoromethyl (CF3), fiuoromethyl, trif!uoroethyl, 2-fluoropropyl, 3,3,3-trif!uoropropyi, 4,4,4- trifluor
• Haiogenated carbocyclic groups include fluorinated cycioalkyl groups such as 2,2-difiuorocyciopropyl, 2,3-dif!uorocyc!obutyl, 3,4- difluorocyclohexyi, and 3,4-difiuoro-5-methylcyclohepty!; and chlorinated cycioalkyl groups such as 2,2-dichiorocyclopropyi, 2,3-dich!orocyclopentyl.
• Haloaikenyl groups include ally! chloride.
• 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- 1Jun12.pdf, except carbon.
• 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 acyi, amide, amine, carboxyi, cyano, epoxy, hydrocarbonoxy, imino, ketone, ketoxime, mercapto, oxime, and/or thiol.
• the heteroatom containing group may be a haiogenated hydrocarbon group as defined above.
• the heteroaiom containing group may be a hydrocarbonoxy group such as an alkoxy group or an alkyiaikoxy 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, su!fonyl, 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 aikyl groups in which at least one carbon atom has been replaced with a heteroatom such as N, G, P, or S, e.g., when the heteroatom is O, the heteroaikyi 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.
• Heterocycies may be monocyclic or alternatively may be fused, bridged, or spiro poiycyclic rings.
• Monocyclic heterocycies may have 3 to 9 member atoms in the ring, alternatively 4 to 7 member atoms, and alternatively 5 to 6 member atoms.
• Poiycyclic heterocycies may have 7 to 17 member atoms, alternatively 7 to 14 member atoms, and alternatively 9 to 10 member atoms.
• Heterocycies 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.
• Poiycyclic 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 heteroara!kyl, i.e., an aikyl group having a pendant and/or terminal heteroaryl group or a heteroaryl group having a pendant aikyl group.
• exemplary heteroaralkyi groups include 6- methylpyridyl and dimethylpyridyl.
• cP centiPoise
• cSt centiStokes
• DP centiStokes
• FTIR Fourier transform infrared spectroscopy
• GC gas chromatography
• GPC gel permeation chromatography
• M n means number average molecular weight.
• M n may be measured using GPC.
• M w means weight average molecular weight.
• N R means nuclear magnetic resonance.
• Pa-s means Pascal seconds, and "ppm” means parts per million.
• COD means cyclooctadienyi.
• Et means ethyl.
• Me means methyl.
• Ph means phenyl (i.e., substituted or unsubstituted phenyl groups).
• Pr means propyl and includes various structures such as sPr and rtPr.
• iPr” or “'Pr” means isopropyl.
• nPr means normal propyl.
• Bu means butyl and includes various structures including nBu, sec-butyl, tBu, and SBu.
• iBu or " ! Bu” 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 siioxane unit having formula F ⁇ SiO- j ⁇ , where each R independently represents a monovalent atom or organic group.
• D-unit means a siioxane unit having formula 3 ⁇ 4 ⁇ '3 ⁇ 4/2' wn s e each R independently represents a monovalent atom or group.
• T-unit means a siioxane unit having formula RSiC ⁇ , where each R independently represents a monovalent atom or group.
• Q-urtit means a siioxane unit having formula SiO ⁇
• Non-functional means that the component does not have either an aiiphatica!iy unsaturated substituent or a silicon bonded hydrogen atom that could participate in a hydrosiiylation reaction.
• the composition described herein may be free of platinum catalysts.
• Tree of platinum catalysts means that the composition contains a non-detectable amount of a platinum catalyst capable of catalyzing a hydrosiiylation reaction with the unsaturated groups on other components 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.
• Tree of conventional metal catalysts means that the composition contains a non-detectable amount of a the metal selected from Pt, Rh, Pd, and Os, or the compound of such a metal capable of catalyzing a hydrosiiylation reaction with the unsaturated groups on other components 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 hydrosiiylation reaction catalysts (i.e., free of any component capable of catalyzing a hydrosiiylation reaction of the aliphaticaily unsaturated groups on component (B), described below, other than component (A) described herein).
• the present invention discloses ligand components, and reaction products including the ligand components.
• the present invention also discloses, in certain embodiments, an activated reaction product including the reaction product combined with an ionic activator.
• the present invention relates the activated reaction productsthat are useful as hydrosi!ylation catalysis, and compositions that utilize the activated reaction products, as will be described in further detail below.
• each Ph is a substituted or unsubstituted phenyl group
• each Cyc is a substituted or unsubstituted cycloaikyl group
• X is an unsubstituted arylene or a C2-C3 substituted or unsubstituted aikylene
• R ⁇ is H, methyl or Ph
• Y is pyridyl or 6-phenylpyridy!
• R ⁇ is a C- j -C- j Q substituted or unsubstituted alkyl group, such as a C2-C substituted or unsubstituted alkyl group, such as a C3 or C substituted or unsubstituted alkyl group.
• the ligand component of formula (1 ) is further defined according to any one or more of formulas (1A)-(1 I) below:
• Formuias (1 A)-(11) above may alternatively be referred to herein by their respective PNN designation, the designations of which are described at the beginning of the Examples Section below. More specifically, Formula (1A) above may alternatively be referred to as pAr N Me N . Formu
• the ligand component in accordance with the present invention, may be produced by treating a phosphino-group containing component according to the formula (3) with a pyridine-contairiing component according to formula (4):
• the phosphino-group containing component according to the formula (3) is further defined according to any one or more of formuias (3A)-(3D) below: Ph 2 P ⁇ * -' iSiH 2 (3B);
• Ph is an unsubstiiuted phenyl group
• Cy is an unsubstituted cyclohexy! group
• iPr is an isopropyi group.
• the pyridine-containing component according to formula (4) is further defined according to any one or more of formulas (4A)-(4E) below:
• the present invention is also directed to reaction products that include the iigand component, in accordance with any embodiment above, and a metal precursor.
• the present invention is also directed to the associated methods for preparing these reaction products.
• the metal precursor, or M precursor may be a metal compound having general formula (2): [ - ⁇ ] ⁇ , where
• M is a metal atom selected from the group consisting of iron (Fe), cobalt (Co), manganese (Mn), nickel (Ni), zinc (Zn) and ruthenium (Ru);
• each A is independently a dispiaceabie substituent
• subscript x is an integer with a value ranging from 1 to the maximum valence number of the metal atom selected for ;
• n 1 or 2.
• the M precursor may have any one of formulas (a), (b), (c), (d), or (e).
• formula (a) is [Fe-A x ]
• formula (b) is [Co ⁇ A x ]
• formula (c) is [Mn-A x ]
• formula (d) is [Ni-A x ]
• formula (e) is [Ru-A ⁇ .
• M may be any one of Fe, Co, Mn, Ni and Ru.
• each instance of A in the general formula for the M precursor 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, siiazane groups, carboxylate groups, carboxyiic ester groups, carbonyi groups, hydrocarbonoxy groups, sulfonate ester groups, sulfortyiimide groups, acetate groups, and cyano groups.
• Examples of halogen atoms for A in the general formula (2) for the M precursor include Br, CI, or I.
• monovalent halogenated hydrocarbon groups for A in general formula (2) include haioalkyl groups, e.g., fluorinated aikyi groups such as CF3, fluoromethyl, trifluoroethyl, 2-fiuoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyi, 4,4,4,3,3- pentafluorobuty!, 5,5,5,4,4,3,3-heptafluoropentyi, 6,6,6,5,5,4,4,3,3-nonafiuorohexyl, and 8,8,8,7,7-pentaf!uoroocty!; and chlorinated alkyl groups such as ch!oromethy!
• halogenated carbocyclic groups such as fluorinated cycloaikyl groups such as 2,2-difluorocycIopropyl, 2,3-difIuorocyclobutyi, 3,4-dif!uorocyc!ohexyi, and 3,4-difluoro-5- methy!cycioheptyl; and chlorinated cycloaikyl groups such as 2,2-dich!orocyc!opropyl, 2,3- dichiorocyciopentyi; and haioalkenyi groups such as ally! chloride.
• Examples of monovalent hydrocarbon groups for A in the general formula (2) for the M precursor include, but are not limited to, aikyl, alkenyl, carbocyclic, aryi, and aralkyl, Aikyl groups are exemplified by Me, Et, Pr, Bu, perttyl, hexyi, heptyl, ethylhexyi, octyl, decy!, dodecyi, undecyi, and octadecyl.
• Alkenyl groups are exemplified by VI, allyl, propenyl, and Hex.
• Carbocyclic groups are exemplified by saturated carbocyclic groups, e.g., cycioaikyl such as cyclopentyl and cyclohexyl, or unsaturated carbocyclic groups, e.g., cycioalkenyl such as cyciopentadienyl, cyclohexeny!, or cyc!ooctadienyi.
• Aryi groups are exemplified by Ph, tolyl, xyiyi, mesityl, and naphthyl.
• Aralkyl groups are exemplified by benzyl and 2- pheny!ethyl.
• Examples of amino groups for A in the general formula (2) for the M precursor 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, alky!
• each A ' may be a hydrogen atom or an a
• each A in the general formula (2) for the M precursor may be a siiazane group.
• each A in the general formula for the M precursor may be a carboxylic ester group.
• suitable carboxylic ester groups for A include, but are not limited to OAc, efhylhexanoate (such as 2-EHA), neodecanoate, octanoate, and stearate.
• Examples of monovalent hydrocarbonoxy groups for A in the general formula (2) for the M precursor may have formula -OA", where A" is a monovalent hydrocarbon group.
• Examples of monovalent hydrocarbon groups for A" include, but are not limited to, aikyl such as Me, Et, Pr, Bu, pentyl, hexyi, heptyl, ethylhexyi, octyl, decyl, dodecyi, undecyi, and octadecyl; alkenyl such as VI, allyl, propenyl, and Hex; cycioaikyl such as cyclopentyl and cyclohexyl; aryi such as Ph, tolyl, xy!yl, and naphthyl; aralkyl such as benzyl or 2- phenylethyl.
• each A" may be an aikyl group, such as Me, Et, nPr, iPr, nBu, iBu, or tBu.
• each A" may be an aikyl group, and alternatively each A" may be Et, Pr such as iPr or nPr, or Bu.
• each A in the general formula (2) for the M precursor may be an aikyl group, such as Me, Et, nPr, iPr, nBu, iBu, or tBu.
• each A may be independently selected from the group consisting of Et, benzyl mesity!, Ph, NEt2, NIV ⁇ , cyclooctadiene, ethoxide, iPr, Bu, 2-EHA, ethoxy, propoxy, methoxy, and carbonyl.
• the M precursor may be a commercially or synthetically available compound, such as those shown below in Table 1 .
• Sigma-AIdrich refers to Sigma-Aldrich, Inc. of St. Louis, Missouri, U.S.A., and
• the metal precursor may be iron (ii) bromide, cobalt
• reaction product (of formula (2) with formula (1 )) is further defined according to any one or more of formulas (2A)-(2H) below:
• each Ph is an unsubsiituted phenyl group.
• Formulas (2A) ⁇ (2G) may alternatively be referred to by their respective metal complex - PNN designation. More specifically, Formula
• Formula (2A) above may alternatively be referred to as Co(P ⁇ r ⁇ e )Ci2;
• Formula (2B) above may alternatively be referred to as Formula (2C) above may alternatively be referred to as Co(P Ar n N)Ci2;
• Formula (2D) above may alternatively be referred to as
• Co(P Pr N Ph N)CI 2 may alternatively be referred to as Co(P Et N H N)CI;
• Formula (2F) above may alternatively be referred to as Co(P ⁇ N ⁇ N)Me; Formula (2G) above may alternatively be referred to Co(P Ar N ⁇ N)CI 2 ; and Formula (2H) above may alternatively be referred to as of Co PrP Pr ⁇ Cl2-
• the reaction product is activated to form an activated reaction product ⁇ i.e., a catalyticaliy active reaction product).
• the activated reaction product as will be described in further detail below, is useful as a hydrosilyiation catalyst.
• activating the reaction product can be performed by reducing the formal oxidation state of the metal atom in the reaction product by combining the reaction product described above with a reducing agent.
• reducing agents that may be combined with the reaction product include an alkali metal amalgam; hydrogen, a metal hydride such as lithium aluminum hydride (LiA!H ⁇ ) or sodium naphtha!enide; a silyl hydride (which may be in addition to, or instead of, ail or a portion of a siiane cross!inker, described below); or a metai borohydride such as sodium triethyiborohydride ( aEt3BH), lithium triethyiborohydride (LiEt jBH), or sodium borohydride (NaBh ⁇ ).
• Suitable reducing agents include those described in Chem. Rev. 1996, 96, 877-910.
• reaction product described above can be activated by a process comprising combing the reaction product described above with an ionic activator.
• ionic activators for use in the reaction product include carboranes, such as
• metal borates such as lithium tetrakis(pentaf!uoropheny!borate (LiBArF), lithium tetrakis(3,5- trifluoromethy!phenylborate, sodium tetrakis(3,5-trifluoromethyi)phenylborate, or a mixture thereof.
• Additional suitable ionic activators may also include ionic activators that include silicon atoms.
• ionic activators that include silicon atoms.
• Still further examples of other suitable ionic activators include, but are not limited to, CH3U, BuLi, PhLi, eMgCI, eMgBr, and (ailyi)MgBr.
• compositions that include at least one component capable of undergoing a hydrosilylation reaction.
• composition which has at least one component capable of reacting by hydrosilylation reaction (composition) comprises:
• the activated reaction product 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 siiane, a gum, a gel, a rubber, and a resin.
• the composition further comprises component (C), an SiH functional compound having an average, per molecule, of one or more silicon bonded hydrogen atoms, which is distinct from components (A) and (B).
• the composition may optionally further comprise one or more additional components, which are distinct from component (A), component (B), and component (C) described above.
• additional components are exemplified by (D) a spacer; (E) an extender, a piasticizer, 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 !engthener; (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 any combination thereof.
• Component (A) may be prepared by a method comprising combining the iigand component and the precursor, as described above.
• the method may optionally further comprise a step of dissolving either the M precursor, or the iigand component, or both, in a solvent before combining the M precursor and the iigand component.
• Suitable solvents are exemplified by those described below for component (S).
• the Iigand component may be dissolved in a solvent in a container, and the solvent may thereafter be removed before adding the M precursor to the container with the Iigand component.
• the amounts of Iigand component and precursor are selected such that the mole ratio of Iigand compoent to M precursor (Metal: Ligand Component 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 Component 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 M precursor and the ligand component may be performed by any convenient means, such as mixing them together in or shaking the container.
• the reaction of the M precursor and ligand component may be performed by under any convenient conditions such as allowing the M precursor and iigand component prepared as described above to react at -80°C to 200°C, alternatively room temperature (RT) of 25°C 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, aiternatively 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.
• RT room temperature
• the compiexation reaction temperature depends on various factors including theinc!uding solubilities of the components and reactivities of the specific M precursor and ligand component selected and the Metal: Ligand Component Ratio, however, temperature may range from 25°C to 200 °C, alternatively 25 °C to 75 °C.
• Compiexation reaction time depends on various factors including the reaction temperature selected, however, compiexation reaction time may typically range from 1 second (s) to 48 hours (h), alternatively 1 minute (min) to 30 hours (h), and alternatively 45 minutes to 15 hours.
• the iigand component and M precursor may be combined and heated sequentially. Alternatively, the ligand component and M precursor may be combined and heated concurrently.
• the method of preparing the catalytical!y active reaction product of component (A) further comprises activating the reaction product prepared as described above with thereducing agent or the ionic activator.
• the activated reaction product is formed prior to being combined with component (B) (wherein component (B) contains a silicon bonded hydrogen atom) or components (B) and (C) (when component (B) does not contain a silicon bonded hydrogen atom) of the composition.
• the activated reaction product is formed in situ with component (B) (wherein component (B) contains a silicon bonded hydrogen atom) or is formed in situ with components (B) and (C) (when component (B) does not contain a silicon bonded hydrogen atom) of the composition.
• component (B) wherein component (B) contains a silicon bonded hydrogen atom
• components (B) and (C) when component (B) does not contain a silicon bonded hydrogen atom
• the method of preparing the caiaSyticaily active reaction product of component (A) may optionally further comprise adding a solvent after the reaction. Suitable solvents are exemplified by those described below for component (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 M precursor and the iigand before or during the comp!exation reaction.
• By-products include, for example, H-A (where A is as defined above in the general formula for the M precursor) or any species resulting from reacting a disp!aceable substituent off the M precursor when the Iigand reacts with the M 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 M-!igand complex may be used as the catalyticaily active reaction product of component (A).
• the reaction by-products are not removed before using the activated reaction product as component (A).
• the Iigand component and M precursor may be reacted as described above, with or without solvent removal, and then combined with the ionic activator, and the resulting activated reaction product (comprising the activated reaction product and the reaction by-product and optionally a solvent or diluent) may be used as component (A).
• a byproduct may act as a hydrosilylation reaction catalyst, or as a co-catalyst or an activator, in addition to the activated reaction product. Therefore, the reaction by-product may also catalyze the hydrosilylation reaction.
• the composition may contain one single catalyst.
• the composition may comprise two or more catalysts described above as component (A), where the two or more catalysts differ in at least one property such as selection of ligand component, selection of M precursor, Metal: Ligand Component Ratio, and definitions for group A in the general formula (2) for the M precursor.
• the composition may be free of platinum catalysts.
• the composition may be free of conventional metal catalysts.
• the composition may be free of any M compound that would catalyze the hydrosilyiation reaction of the unsaturated groups on component (B) other than the component (A).
• the composition may be free of hydrosilyiation reaction catalysts other than component (A).
• the composition may be free of any component that would catalyze the hydrosilyiation reaction of the unsaturated groups on component (B) other than component (A).
• Component (A) is present in the composition in a catalytically effective amount. The exact amount depends on various factors including reactivity of component (A), the type and amount of component (B), and the type and amount of any additional component, if present. However, the amount of component (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 components in the composition.
• ppm part per million
• Component (B) is an aliphaticaily unsaturated compound having an average, per molecule, of one or more aliphaticaily unsaturated organic groups capable of undergoing hydrosilyiation reaction.
• component (B) may have an average of two or more aliphaticaily unsaturated organic groups per molecule.
• the aliphaticaily unsaturated organic groups may be aikenyl exemplified by, but not limited to, vinyl, ally!, propenyl, butenyi, and hexenyi.
• the unsaturated organic groups may be alkynyl groups exemplified by, but not limited to, ethynyl, propyrtyl, and butynyl.
• Component (B) of the composition may be an unsaturated hydrocarbon, where the unsaturated group is capable of reacting via hydrosilyiation reaction.
• Component (B) may be monomeric.
• suitable aliphaticaily unsaturated organic compounds for component (B) include, but are not limited to alkenes such as ethylene, propene, 1 -butene, 2-butene, 1-pentene, 1-hexene, 1-heptene; haiogenated alkenes, such as allyl chloride: diolefins such as divinyibenzene, butadiene, 1 ,5-hexadiene, and 1-buten-3-yne; cycioolefins such as cyclohexene and cycioheptene; and aikynes such as acetylene, propyne, and 1- hexyne.
• Oxygen-containing a!iphatical!y unsaturated compounds can also be used for component (B), for example, where the unsaturation is ethy!enic, such as vinylcyclohexyi epoxide, a!!yl glycidyi ether, methy!viny! ether, divinyiether, phenylvinyl ether, monoa!ly! ether of ethylene glycol, ally! aldehyde, methylvinyl ketone, phenylvinyl ketone, acrylic acid, methacrylic acid, methyl acryiate, aliyl acrylate, methyl methacrylate, ally! methacrylate, vinyiacetic acid, vinyl acetate, and linolenic acid.
• ethy!enic such as vinylcyclohexyi epoxide, a!!yl glycidyi ether, methy!viny! ether, divinyiether
• Heterocyclic compounds containing aliphatic unsaturation in the ring are also suitable as component (B).
• Unsaturated compounds containing nitrogen substituents such as acrylonitrile, N-vinyipyrro!idone, alkyi cyanide, nitroethylene are also suitable as component (B).
• component (B) of the composition comprises a polymer.
• Component (B) may comprise a base polymer having an average of one or more aliphaticaily unsaturated organic groups, capable of undergoing a hydrosiiyiafion reaction, per molecule.
• Component (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 oiefinic monomers having 2 to 20 carbon atoms and dienes having 4 to 20 carbon atoms; polymers of monoo!efin, isomonoolefin and vinyl aromatic monomers, such as monoolefins having 2 to 20 carbon groups, isomonooiefins having 4 to 20 carbon groups, and vinyl aromatic monomers including styrene, para-a!ky!styrene, para-methylstyrene.
• the compounds can be poly(dienes). Most polymers derived from dienes usually contain unsaturated ethy!enic units on backbone or side-chains.
• Representative examples include polybutadiene, polyisoprene, polybutenylene, poly(aikyi-buteny!ene) where alky! includes aikyl groups having 1 to 20 carbon atoms, poly(phenyl-huteny!ene), poiypentenyiene, natural rubber (a form of polyisoprene); and butyl rubber (copolymer of isobuty!ene and isoprene).
• component (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 benzyiic halogen, halogenated poiybutadienes, halogenated po!yisobutylene, poly(2-ch!oro ⁇ 1 ,3-butadiene), poiychioroprene
• component (B) may comprise polymers containing other compounds described above such as vinyl ether groups, acryiate groups, methyacrylate groups, and epoxy-functiona! groups.
• component (B) may comprise a silane having aliphatic unsaturation.
• the silane may have a general formula of: R ⁇ xx SiR ⁇ (4_ xx j, where subscript xx is an integer from 1 to 4, alternatively 1 to 3, and alternatively 1. is an aiiphaticaliy unsaturaged organic group, and is selected from H, a halogen atom, and aa monovalent organic group.
• component (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 homopo!ymer or a copolymer.
• Component (B) may be one base polymer.
• component (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 aiiphaticaliy 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 component (B) may be monovalent organic groups free of aliphatic unsaturation.
• monovalent hydrocarbon groups include, but are not limited to, aikyl such as Me, Et, Pr, Bu, pentyi, hexyi, heptyi, octyl, decyi, dodecyl, undecy!, and octadecyi; cycioaikyl such as cyclopentyi and cyclohexyi; ary!
• halogenated hydrocarbon groups include, but are not limited to, chlorinated alky!
• chloromethyi and chioropropyl groups such as chloromethyi and chioropropyl groups; fluorinated aikyl groups such as f!uoromethy!, 2-fiuoropropyi, 3,3,3- trifiuoropropyi, 4,4,4-trifluorobutyi, 4,4,4, 3,3-pentafluorobutyl, 5,5, 5,4,4,3, 3-heptafIuoropenty!, 6,6,6,5,5,4,4,3,3-nonafiuorohexy!, and 8,8,8,7,7-pentafluoroocty!; chlorinated cycioaikyl groups such as 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl; and fluorinated cycioaikyl groups such as 2,2-difluorocyclopropyl, 2,3-difiuorocyciobuty
• Examples of other monovalent organic groups include, but are not limited to, hydrocarbon groups substituted with oxygen atoms such as glycidoxyaikyi, and hydrocarbon groups substituted with nitrogen atoms such as aminoalkyi and cyano- functional groups such as cyanoethyl and cyanopropyl.
• Component (B) may comprise a polydiorganosiioxane of Formula (I): R 41 2 42 SiO(R 41 2S!0) a (R 41 R 42 SiO) b S!R 41 2 42 , Formula (II): R 41 3SiO(R 41 2S!0) c (R 41 42 SiO) d SiR 41 3l or a combination thereof, in Formulae (I) and
• each R ⁇ is independently a hydrogen atom or a monovalent organic group free of aliphatic unsaturation and each R 42 is independently an aiiphaticaiiy 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.
• subscript d may have an average value ranging from 2 to 2000.
• Suitable monovalent organic groups for R 4 ⁇ are as described above for component (B).
• each R 4 ⁇ is a monovalent hydrocarbon group exemplified by alkyl such as Me and aryl such as Ph.
• Each R 42 is independently an aiiphaticaiiy unsaturated monovalent organic group as described above for component (B).
• R * is exemplified by aikenyl groups such as vinyl, ally!, butenyl, and hexenyl; and alkynyl groups such as ethynvi and propynyl.
• Component (B) may comprise a polydiorganosiloxane such as
• component (B) may further comprise a resin such as an MQ resin consisting essentially of R ⁇ SiG ⁇ units and S1O4/2 units, a TD resin consisting essentially of R3 ⁇ 4iC>3/ units and R ⁇ SiC ⁇ units, an MT resin consisting essentially of R ⁇ jSiO ⁇ units and R ⁇ SiO- ⁇ units, an MTD resin consisting essentially of R ⁇ gSiO- j ⁇ units, R3 ⁇ 403/2 units, and R ⁇ SiC ⁇ units, or any combination thereof.
• a resin such as an MQ resin consisting essentially of R ⁇ SiG ⁇ units and S1O4/2 units, a TD resin consisting essentially of R3 ⁇ 4iC>3/ units and R ⁇ SiC ⁇ units, an MT resin consisting essentially of R ⁇ jSiO ⁇ units and R ⁇ SiO- ⁇ units, an MTD resin consisting essentially of R ⁇ gSiO- j ⁇ units, R3 ⁇ 403/2 units, and R ⁇
• Each R° is a monovalent organic group exemplified by those described above for component (B).
• the monovalent organic groups represented by R ⁇ may have
• examples of monovalent organic groups for R ⁇ include, but are not limited to, monovalent hydrocarbon groups and monovalent haiogenated hydrocarbon groups.
• the resin may contain an average of 3 to 30 mole percent of aiiphaticaliy unsaturated organic groups, alternatively 0.1 to 30 mole percent, alternatively 0.1 to 5 mole percent, alternatively 3 to 100 mole percent.
• the aiiphaticaliy unsaturated organic groups may be aikenyl groups, alkynyi groups, or a combination thereof.
• the mole percent of aiiphaticaliy unsaturated organic groups in the resin is the ratio of the number of moles of unsaturated group-containing siioxane units in the resin to the total number of moles of siioxane units in the resin, multiplied by 100.
• resin may be prepared by treating a resin copolymer produced by the silica hydrosoi capping process of Daudt, et a/, with at least an aikenyl-containing endbiocking reagent.
• the method of Daudt et a/. is disclosed in U.S. Patent 2,676,182.
• the method of Daudt, et al. involves reacting a silica hydrosoi under acidic conditions with a hydro!yzab!e triorganosilane such as trimethylchiorosiiane, a siioxane such as hexamethyidisi!oxane, 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.
• the resin which typically contains less than 2 % of silicon-bonded hydroxyl groups, may be prepared by treating the product of Daudt, et a/, with an unsaturated organic group- containing endbiocking agent and an endbiocking 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.
• endbiocking agents include, but are not limited to, siiazanes, siioxanes, and silanes. Suitable endbiocking agents are known in the art and exemplified in U.S. Patents 4,584,355; 4,591 ,622; and 4,585,836. A single endbiocking agent or a mixture of such agents may be used to prepare the resin.
• component (B) may comprise a silicon containing base polymer other than the polyorganosi!oxanes described above.
• other compounds suitable for component (B) include siiazanes and/or polymeric materials containing silicon atoms joined together by hydrocarbyl groups such as aikylene or polyalkylene groups or aryiene groups.
• the silicon-modified organic compounds useful as component (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.
• siiicon-modified organic polymers for component (B) are exemplified by, but not limited to aikenylsiloxy-functionai polymers such as viny!si!oxy-, ailylsiloxy-, and hexertyisiioxy- organic polymers and siloxane-organic block copolymers.
• silane-modified organic polymers are siiyiated polymers derived from olefins, isomonoolefin, dienes, ethylene or propylene oxides, and vinyl aromatic monomers having 2 to 20 carbon atoms such as the si!ane-grafted copolymers of isomonoolefin and vinyl aromatic monomers.
• Examples of silicon-modified organic polymers described by above include vinylsi!oxy-terminated or hexenyisiloxy-terminated po!y(dimethyisiloxane/hydrocarbyi) copolymers, viny!siloxy-termirtated or hexenyisiloxy-terminated poly(dimethylsi!oxane/polyoxyalkyiene) block copolymers, alkenyloxydimethylsiioxy- terminated polyisobuty!ene and alkenyioxydimethylsiloxy-terminated polydimethylsiloxane/polyisobuty!ene block copolymers.
• suitable compounds for component (B) may be found, for example, in WO 2003/093369.
• the amount of component (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 aiiphaticaliy unsaturated groups of component (B), the type and amount of component (A), and the content of silicon bonded hydrogen atoms of, component (B) and/or component (C). However, the amount of component (B) may range from 0.1 % to 99.9 % based on the weight of all components in the composition.
• Component (C) in the composition is a Si-H functional compound, i.e. , a compound having an average, per molecule, of one or more silicon bonded hydrogen atoms.
• Component (C) may comprise a silane and/or an organohydrogensi!icon compound.
• component (C) may have an average, per molecule, of at least two silicon- bonded hydrogen atoms.
• the amount of component (C) in the composition depends on various factors including the SiH content of component (C), the unsaturated group content of component (B), and the properties of the reaction product of the composition desired, however, the amount of component (C) may be sufficient to provide a molar ratio of SiH groups in component (C) to aiiphaticaliy unsaturated organic groups in component (B) (commonly referred to as the SiH: Vs ratio) ranging from 0.3:1 to 5:1 , alternatively 0.1 :10 to 10:1.
• Component (C) can have a monomeric or polymeric structure. When component (C) has a polymeric structure, the polymeric structure may be linear, branched, cyclic, or resinous structure.
• component (C) When component (C) is polymeric, then component (C) can be a homopo!ymer or a copolymer.
• the silicon-bonded hydrogen atoms in component (C) can be located at terminal, pendant, or at both terminal and pendant positions.
• Component (C) may be one SiH functional compound.
• component (C) may comprise a combination of two or more SiH functional compounds.
• Component (C) may be two or more organohydrogenpoiysi!oxanes that differ in at least one of the following properties: structure, average molecular weight, viscosity, siloxane units, and sequence.
• component (C) may comprise a silane of formula (5): R 4 e SiH
• 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, aikyl such Me, Et, Pr, Bu, pentyl, hexyl, heptyl, octyl, decyl, dodecyi, undecyl, and octadecy!; cycloalkyl such as cyclopentyi and cyciohexyl; aryi such as Ph, toiyl, xyiyl, and naphthyl; and araikyl such as benzyl, 1-phenyletby! and 2-phenyiethy!.
• aikyl such Me, Et, Pr, Bu, pentyl, hexyl, heptyl, octyl, decyl, dodecyi, undecyl, and octadecy!
• cycloalkyl such as cyclopentyi and cyciohexyl
• Examples of monovalent halogenated hydrocarbon groups include, but are not limited to, chlorinated alkyl groups such as chioromethyl and chloropropy! groups; fiuorinated alkyl groups such as f!uoromeihyi, 2-fluoropropyI, 3,3,3- tnfluoropropyl, 4,4,4-trifluorobutyi, 4,4.4,3.3-pentafluorobutyl, 5, 5,5,4,4, 3,3-heptafluoropentyi, 6,6,6,5,5,4,4,3,3-nonaf!uorohexy!, and 8,8,8,7,7-pentaf!uorooctyl; chlorinated cycloa!kyl groups such as 2,2-dichlorocyclopropyi, 2,3-dichiorocyciopentyl; and fiuorinated cycioalkyl groups such as 2,2-difluorocyclopropy!, 2,3-difluor
• 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 meihoxy, ethoxy, propoxy, and butoxy; and hydrocarbon groups substituted with nitrogen atoms such as aminoalkyi and cyano-fu nctiona! groups such as cyanoethyi and cyanopropy!.
• suitable siianes for component (C) are exemplified by trich!orosilane (HSiCI 3 ), Me 2 HSiCI, or MeHSi(O e) 2
• the organohydrogensilicon compound of component (C) may comprise a polyorganohydrogensiloxane comprising siloxane units including, but not limited to,
• each R° is independently selected from the monovalent organic groups free of aliphatic unsaturation described above.
• component (C) may comprise a polyorganohydrogensiloxane of Formula (III): R ⁇ 3 SiO(R ⁇ 2 SiO)g(R ⁇ HSiO) 1 SiR ⁇ 3 ; Formula (III): R ⁇ 3 SiO(R ⁇ 2 SiO)g(R ⁇ HSiO) 1 SiR ⁇ 3 ; Formula (III): R ⁇ 3 SiO(R ⁇ 2 SiO)g(R ⁇ HSiO) 1 SiR ⁇ 3 ;
• 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
• Each R 3 ⁇ 4 is independently a monovalent organic group, as described above.
• the organohydrogensilicon compound of component (C) may comprise a com ound of formula (V):
• each R y 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 3 ⁇ is independently selected from a monovalent organic group a halogen atom or a siloxane unit as described in the sections above.
• each R 3 ⁇ is a functional group independently selected from a halogen atom, an ether group, an aikoxy group, an alkoxyether group, an acyl group, an epoxy group, an amino group, a silyl group, or a --Z-R 3 ⁇ group, where each Z is independently selected from an oxygen atom and a divalent hydrocarbon group comprising 2 to 20 carbon atoms, each R 3 ⁇ group is independently selected from -BR U R ⁇ -u- " ⁇ ' R29 v R 2 g_ v , or a group described by formula (VI):
• each R 29 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
• R y and R dU 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 groups is replaced by the Z group bonding the group to the cyc!osiloxane of formula (VII), and provided further if aa+bb+cc+dd>0 then w+x+y+z>0.
• organohydrogertsiiicori compounds are commercially available and methods for their preparation are exemplified in WO2003/093349 and WO2003/093369.
• An exemplary organohydrogensilicon compound may have the general formula:
• each is independently selected from a hydrogen atom and a monovalent organic group
• each R ⁇ 4 is independently selected from a hydrogen atom, a monovalent organic group, and a group of formula: ; subscript bh 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.
• at least one instance of is a hydrogen atom.
• Suitable monovalent organic groups for R 0 ° and/or R° 4 are exemplified by those groups described above for R 2 ⁇ .
• component (C) in the composition depends on various factors including reactivity of component (A), the type and amount of component (B), whether component (B) contains a silicon bonded hydrogen atom, and the type and amount of any additional component (other than component (C)), if present.
• the amount of component (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 components in the composition.
• Component (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 from25 micrometers ( ⁇ ) to125 ⁇ . 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 component (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 component (D) ranging from 0.05 % to 2 %, alternatively 0.1 % to 1 %.
• Component (E) is an extender and/or a plasticizer.
• An extender comprising a non-functional polyorganosiioxane may be used in the composition.
• the nonfunctional poiyorganosiloxane may comprise difunctionai units of the formula: R3 ⁇ 43 ⁇ 43 ⁇ 4/2 and terminal units of the formula: R ⁇ SiR ⁇ -, where each R ⁇ and each R ⁇ are independently a monovalent organic group such as a monovalent hydrocarbon group exemplified by alkyi such as methyl, ethyl, propyl, and butyl; alkenyl such as vinyl, aliyi, and hexenyi; aryl such as Ph, toiyl, xylyl, and naphthyi; and aralkyl groups such as phenylethyi; and R ⁇ 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 may be a divalent organic group, a silicone organic group, or a combination of a divalent hydrocarbon group and a divalent siloxane group.
• each m ay be independently selected from an oxygen atom and a divalent hydrocarbon group.
• each R ⁇ may be an oxygen atom.
• each R ⁇ may be a divalent hydrocarbon group exemplified by an aikyiene group such as ethylene, propylene, butylene, or hexy!ene; an arylene group such as
• an instance of R o may be an oxygen atom while a different instance of is a divalent hydrocarbon group.
• Non-functional po!yorganosiloxanes are known in the art and are commercially available. Suitable non-functional poiyorganosiioxanes are exemplified by, but not limited to, po!ydimethyisiioxanes. Such poiydimethylsiioxanes include DOW CORNING ⁇ ' 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 100,000 cSt, alternatively 50 cSt to 50,000 cSt, and alternatively 12,500 cSt to 60,000 cSt,
• An organic piasticizer may be used in addition to, or instead of, the nonfunctional polyorganosiioxane extender described above.
• Organic p!asticizers are known in the art and are commercially available.
• the organic piasticizer may comprise a phthaiate, a carboxyiate, a carboxyiic acid ester, an adipate or a combination thereof.
• the organic piasticizer may be selected from the group consisting of: bis(2-ethylhexy!) terephthalate; bis(2-ethyihexyi)-1 ,4-benzenedicarboxylate: 2-ethyihexyl methyl- 1 ,4-benzenedicarboxylate; 1 ,2 cyciohexanedicarboxyiic acid, dinonyi ester, branched and linear; bis(2-propyiheptyl) phthaiate; diisononyl adipate; and a combination thereof.
• R" 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 alky! group of 4 to 15 carbon atoms, alternatively 9 to 12 carbon atoms.
• Suitable plasticizers may be selected from the group consisting of adipa es, 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.
• the organic plasticizer may 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 is independently a hydrogen atom or a branched or linear monovalent organic group.
• the monovalent organic group for may be an aikyi group such as Me, Et, or Bu. Alternatively, the monovalent organic group for may be an ester functional group.
• Each R ⁇ 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 phtha!ate such as dibutyi phthalate (Eastman DBP Plasticizer), diheptyl phthalate, di(2-ethylhexyi) phthalate, or diisodecyi phthalate (DIDP), bis(2-propylhepty!) phthalate (BASF Palatinol® DPHP) , di(2- ethylhexyl) phthalate (Eastman DOP Plasticizer), dimethyl phthalate (Eastman DMP
• a dialkyl phtha!ate such as dibutyi phthalate (Eastman DBP Plasticizer), diheptyl phthalate, di(2-ethylhexyi) phthalate, or diisodecyi phthalate (DIDP), bis(2-propylhepty! phthalate (BASF Palatin
• Plasticizer diethyl phthalate (Eastman DMP Plasticizer): butyl benzyl phthalate, and bis(2-ethyihexyl) 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-benzenetricarboxy!ic acid (BASF Paiatinoi® TGTM-I), bis(2- ethylhexyi)-1 ,4-benzenedicarboxy!ate (Eastman 168 Plasiicizer); 2-ethylhexyi methyl-1 ,4- benzenedicarboxylate; 1 ,2 cyclohexanedicarboxylic acid, dinonyl ester, branched and linear (BASF Hexamoil *D!NCH); diisonon
• EH Plasticizer EH Plasticizer
• triacetin Eastman Triacetin
• nonaromatic dibasic acid esters such as dioctyl adipate, bis(2-ethylhexy!) adipate
• EastmanTM DOA Plasticizer EastmanTM DOA
• Plasticizer Kosher
• di-2-ethylhexyiadipate BASF Piastomoil® DOA
• dioctyl sebacate dibutyi sebacate and diisodecyi succinate
• aliphatic esters such as butyl olea e and methyl acetyl recinolate
• phosphates such as tricresyl phosphate and tributyl phosphate
• chlorinated paraffins hydrocarbon oils such as a!kyldipheny!s and partially hydrogertated terpheny!s
• process oils epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate; tris(2-ethy!hexy! ester; a fatty acid ester; and a combination thereof.
• suitable plasticizers and their commercial sources include BASF Palamoil® 652 and
• a polymer plasticizer can be used.
• the polymer plasticizer include alkenyi polymers obtained by polymerizing vinyl or ally! monomers by- means of various methods; polyalkyiene glycol esters such as diethy!ene glycol dibenzoate, triethyiene glycol dibenzoate and pentaerythritol ester; polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azeiaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethyiene glycol, propylene glycol and dipropylene glycol; polvethers including polyeiher 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 poiy-alpha-methyistyrene; and po!y
• the poiyorganosiloxane extenders and organic plasticizers described above for component (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 component (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 component (E) may range from 0.1 % to 10 % based on the combined weights of ail components in the composition.
• Component (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 component (f1 ), 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 component (f1 ) 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
• 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-G-S!L by Cabot Corporation of Massachusetts, U.S.A.
• the composition may optionally further comprise component (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 Ultrapf!ex® and Ultrapflex® 100 from SMI .
• the composition may optionally further comprise component (f3) a conductive filler.
• Component (F) may be both thermally conductive and electrically conductive. Alternatively, component (F) may be thermally conductive and electrically insulating.
• Component (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.
• Component (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 trihyd rate, 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, Ccl, Cu, Pb, Sb, Zn, or a combination thereof.
• meltable fillers examples include Ga, in-Bi-Sn alloys, Sn-in-Zn alloys, Sn-in-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 °C to 250 °C, alternatively! 50 °C to 225 °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 Toyai America, Inc. of Napervclude, Illinois, U.S.A. and Valimet inc., of Stockton, California, U.S.A.
• Silver filler is commercially available from etaior 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.
• Component (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 fiiler. 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.
• the average particle size of the filler will depend on various factors including the type of the filler selected for component (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 pm, alternatively 0.1 to 50 ⁇ , and alternatively 0.1 to 10 pm.
• the amount of component (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 component (B), and the type and amount of the filler selected for component (F). However, the amount of component (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 component (G) a treating agent.
• component (G) a treating agent.
• the amount of component (G) will vary depending on factors such as the type of treating agent selected and the type and amount of particulates (such as components (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.
• component (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 ail components in the composition.
• Particulates such as the fiiler, the physical drying agent, certain flame retardants, and/or certain pigments, when present, may optionally be surface treated with component (G). Particulates may be treated with component (G) before being added to the composition, or in situ.
• Component (G) may comprise an aikoxysilane, an a!koxy-functiona! oiigosiloxane, a cyclic polyorganosiloxane, a hydroxyl-functional oiigosiloxane such as a dimethyl siioxane or methyl phenyl siloxane, or a fatty acid.
• fatty acids include stearates such as calcium stearate.
• organosiiicon filler treating agents that can be used as component (G) include compositions normally used to treat silica fillers such as organochlorosilanes, organosiioxanes, organodisilazanes such as hexaaikyi dssilazane, and organoaikoxysiianes such as CgH ⁇ S QGh ⁇ , C H- j S Q ⁇ Hg ⁇ , C- j r j h ⁇ S QCh ⁇ , c 12 H 25 Si i° CH 3)3> c 14 H 29 Sj (° c 2 H 5)3> and C ⁇ C ⁇ Ct ⁇ S GCh ⁇ .
• Other treating agents that can be used include alkylthiols, fatty acids, titanates, titanate coupling agents, zirconate coupling agents, and combinations thereof.
• component (G) may comprise an aikoxysilane having the formula: R ⁇ m Si(OR ⁇ ) ⁇ 4 tine m ⁇ , where subscript m may have a value ranging from 1 to 3, alternatively subscript m is 3.
• Each ⁇ 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.
• ⁇ is exemplified by alkyl groups such as hexyl, octyl, dodecyi, tetradecyi, hexadecyl, and octadecyi; and aromatic groups such as benzyl and phenylethy!. may be saturated or unsaturated, and branched or unbranched.
• R " ⁇ ⁇ may be saturated and unbranched.
• Each R ⁇ is independently a saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms.
• Alkoxysilanes suitable for use as component (G) are exemplified by hexyltrimethoxysiiane, octyltriethoxysilane, decyltrimethoxysiiane, dodecy!trimethoxysilane, tetradecyltrimethoxysi!ane, phenylethyltrimethoxysi!ane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and combinations thereof.
• Aikoxy-functional oligosiioxanes may also be used as treating agents.
• suitable aikoxy-functional oligosiioxanes include those of the formula (V):
• each R ' 3 may be an alkyl group.
• Each may be an unsaturated monovalent hydrocarbon group of 1 to 10 carbon atoms.
• Each 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 octadecyi mercaptan; fatty acids such as oleic acid and stearic acid; and a combination thereof.
• Treatment agents for alumina or passivated aluminum nitride may include aikoxysilyi functional alkylmethy! polysiioxanes (e.g., partial hydrolysis condensate of
• Other treating agents include aikenyl functional polyorganosiioxanes.
• Suitable aikenyl functional polyorganosiioxanes include, but are not limited to:
• treating agents include mono-endcapped aikoxy functional polydiorganosiioxanes, i.e., polydiorganosiloxanes having an alkoxy group at one end.
• Such treating agents are exemplified by the formula: R» R 26 2Si0(R 26 2Si0)uSi(OR 27 )3 wh ⁇ , ubtajpt u has a v3iue of 0 m aMvely
• Each R ⁇ is independently selected from an alkyl group, such as Me, Et, Pr, Bu, hexyi, and octyi; and an aikenyl group, such as
• Each j s independently an alkyi group such as Me, Et, Pr, Bu, hexyi, and octyi.
• Each R ⁇ is independently an alkyi group such as Me, Et, Pr, and Bu.
• each R ⁇ S, each R ⁇ , and each R ⁇ is Me.
• each R ⁇ 6 and each is Me.
• a polyorganosiioxane 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 compatibi!ization moiety to the filler surface.
• the polyorganosiioxane 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 hydroxy! 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 covarri bonds with the filler.
• the polyorganosiloxane capable of hydrogen bonding may be selected from the group consisting of a saccharide-siloxane polymer, an amirto-functional polyorganosiloxane, and a combination thereof.
• the polyorganosiloxane capable of hydrogen bonding may be a saccharide-siloxane polymer.
• Component (H) is a biocide.
• the amount of component (H) will vary depending on factors including the type of biocide selected and the benefit desired. However, the amount of component (H) may range from greater than 0 % to 5 % based on the weight of all components in the composition.
• Component (H) is exemplified by (hi ) a fungicide, (h2) an herbicide, (h3) a pesticide, (h4) an antimicrobial agent, or a combination thereof.
• Component (hi ) is a fungicide, for example, these include N-substituted benzimidazole carbamate, benzimidazoiyi carbamate such as methyl 2- benzimidazoly!carbamate, ethyl 2-benzimidazoly!carbamate, isopropy!
• Component (h2) is an herbicide
• suitable herbicides include amide herbicides such as aiiidochior N,W-dia!!yl-2-chloroacetamide; CDEA 2 ⁇ chloro- V,N- diethyiacetamide; etnipromid ⁇ f?S)-2-[5-(2,4-dichlorophenoxy)-2-nitrophenoxy]-A - ethylpropionamide; ani!ide herbicides such ascisanilide c s-2,5-dimethy!pyrrolidirte-1 - carboxaniiide; fiufenacet 4'-fluoro-/V-isopropyi-2-[5-(trifiuoromethyi)-1 ,3,4-thiadiazol-2- y!oxy]acetani!ide; naproaniiide (RS)-a-2-naphthoxypropductiiide; arylalanine herb
• 5-c3pyrimidin-2-ylsu!phonamido)benzoic acid metosulam 2',6 -dichloro- 5,7-dimethoxy-3'-methyi[1 ,2.4]triazoio[1 ,5-a]pyrimidine-2-sulphonanilicle; antibiotic herbicides such asbilanafos 4-[hydroxy(methyl)phosphinoyl]-L-homoalanyl-L-alanyi-L- alanine; benzoic acid herbicides such asch!oramben 3-amino-2,5-dichiorobenzoic acid; 2,3,6-TBA 2,3,6-trichiorobenzoic acid; pyrimidinyloxybenzoic acid herbicides such asbispyribac 2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)bertzoic acid; pyrimidiny!thiobenzoic acid herbicides such aspyrithiobac 2-chioro-6-
• cyciopropylisoxazole herbicides such asisoxachiortoie 4-chloro-2-mesy!phenyI 5-cyc!opropyl- 1 ,2-oxazo! ⁇ 4-y! ketone; dicarboximide herbicides such as f!umezin 2-methy!-4-(a,a,a- trifluoro-m-to!yi)-1 .2,4-oxadiazinane-3,5-dione; dinitroaniiine herbicides such asethalfluralin W-ethy!-a,a,a-trifIuoro-A -(2-methylaI!yI)-2,6-dinitro-p-toIuidirie; prodiamine 5-dipropy!amino- a.a ⁇ -trifluoro ⁇ .e-dinitro-o-toluidine; dinitrophenol herbicides such as dinoprop 4,6-dinitro-o- cy
• a,a-trifiuoro-p-toiy!oxy)benzoyi]-L-iactic acid nitropheny! ether herbicides such asaclonifen 2-chioro-6-nitro-3-phenoxyaniline; nitrofen 2,4- dichiorophenyl 4-rtitrophenyl ether; dithiocarbamate herbicides such asdazomet 3,5- dimethyi-1 ,3,5-thiadiazinane-2-thione; halogenated aliphatic herbicides such as dalapon 2,2- dichioropropionic acid; ch!oroacetic acid; imidazolinone herbicides such as imazapyr (RS)-2 ⁇ (4-isopropyl-4-methyI-5-oxo-2-imidazolin-2-yl)nicotinic acid; inorganic herbicides such as disodium tetraborate decahydrate; sodium azide; nitriie herbicides such as chloroxy
• methylthiotriazine herbicides such as cyanatryn 2-(4-ethylamino-6-methy!thio- 1 ,3,5-triazin-2-ylamino)-2-methylpropionitrile
• triazinone herbicides such as hexazinone 3- cyc!ohexyl-6-dimethyiamino-1-methyl-1 ,3,5-triazine-2,4(1 H,3H)-dione
• triazo!e herbicides such as epronaz W-ethyl-A -propyi-3-propyisuiphonyl-1 H-1 ,2,4-triazo!e-1-carboxamide
• triazo!one herbicides such as carfentrazone (RS)-2-ch!oro-3- ⁇ 2-chIoro-5-[4-(difiuoromethyI)-
• triazo!opyrimidine herbicides such as florasuiam 2 , ,6',8-trifluoro-5-methoxy[1 ,2,4]triazolo[1 ,5- c]pyrimidine-2-su!phonani!ide; uracil herbicides such as fiupropacii isopropyi 2-ch!oro-5- (1 ,2.3,6-tetrahydro-3-methy!-2,6-dioxo-4-trifluoromethylpyrimidin-1 -yi)benzoate; urea herbicides such as cycluron 3-cyc!o-octyl-1 -dimethy!urea; monisourori 1-(5-ierf-butyI-1 ,2- oxazoi-3-yi)-3-me
• Component (h3) is a pesticide.
• Suitable pesticides are exemplified by atrazine, diazinon, and ch!orpyrifos.
• pesticide includes insect repellents such as ⁇ , ⁇ -diethy!-meta-toiuamide and pyrethroids such as pyrethrin.
• Component (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.
• component (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
• Component (I) is a stabilizer that may be used for altering the reaction rate of the composition, as compared to a composition containing the same components but with the stabilizer omitted.
• Stabilizers for hydrosilylation curable compositions are exemplified by acetylenic alcohols such as methyl butynoi, ethynyl cyclohexanol, dimethyl hexynoi, and 3,5- dimethyi-1-hexyn-3-o!, 1-butyn-3-oi, 1-propyn-3-o!, 2-methyl-3-butyn-2-ol, 3-methy!-1-butyn- 3-oi, 3-methy!-1-pentyn-3-ol, 3-phenyi-1-butyn-3-ol, 4-ethyl-1-octyn-3-o!, 3,5-diemthyl-1- hexyn-3-ol, and 1-ethyny!-1 -cyclohexan
• component (I) in the composition may be a siiylated acetylenic compound.
• siiylated 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 siiylated acetylenic compound or that contains an organic acetylenic alcohol stabilizer, such as those described above.
• the siiylated acetylenic compound is exemplified by (3-methyl-1-butyn-3- oxy)trimethyisiiane, ((1 ,1 -dimethy!-2-propynyl)oxy)trimethy!siIane, bis(3-methy!-1-butyn-3- oxy)dimethylsi!ane, bis ⁇ 3-methyi-1-butyn-3-oxy)silanemethyiviny!silane, bis((1 , 1 -dimethyI-2- propynyl)oxy)dimethylsilane, methyi(tris(1.1-dimethyl-2-propynyloxy))silane, methy!(fris ⁇ 3- methyl-1-butyn-3-oxy))siIane, (3-methyI-1-butyn-3-oxy)dimethy!phenylsi!ane,
• component (I) is exemplified by methyl(tris(1 ,1-dimethyl-2-propyny!oxy))silane, ((1 ,1-dimethyl-2- propynyl)oxy)trimethylsilane, or a combination thereof.
• the siiylated acetylenic compound useful as component (I) may be prepared by methods known in the art, such as silyiating 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 component (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 ail components in the composition.
• Component (J) is a flame retardant.
• Suitable flame retardants may include, for example, carbon black, hydrated aluminum hydroxide, and silicates such as woilastonite, platinum and platinum compounds.
• the flame retardant may be selected from halogen based flame-retardants such as decabromodipheny!oxide, octabromodiphenyi oxide, hexabromocyclododecane, decabromobiphenyl oxide, diphenyoxybenzene, ethylene bis- tetrabromophtha!mide, pentabromoethy! benzene, pentabromobenzy!
• the flame retardant may be selected from phosphorus based flame
• bicyclic phosphate dimethyl methyl phosphate, phosphine oxide diol, triphenyl phosphate, tris- (2-chloroethyl) phosphate, phosphate esters such as tricreyi, trixylenyi, isodecyl dipheny!, ethylhexyi diphenyl, phosphate salts of various amines such as ammonium phosphate, triocty!, tributyi or tris-butoxyethy! phosphate ester.
• flame retardants may include tetraalkyl lead compounds such as tetraethyl lead, iron pentacarbony!, manganese methyl cyclopentadienyi tricarbonyl, meiamine and derivatives such as meiamine salts, guanidine, dicyandiamide, ammonium sulphamate, alumina trihydrate, and magnesium hydroxide alumina trihydrate.
• tetraalkyl lead compounds such as tetraethyl lead, iron pentacarbony!, manganese methyl cyclopentadienyi tricarbonyl, meiamine and derivatives such as meiamine 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 ail components in the composition.
• Component (K) is a surface modifier.
• Suitable surface modifiers are exemplified by (k1 ) an adhesion promoter and (k2) a release agent.
• Suitable adhesion promoters for component (k1 ) may comprise a transition metal chelate, a hydrocarbonoxysi!ane such as an alkoxysilane, a combination of an a!koxysilane and a hydroxy-functionai polyorganosiloxane, an aminofunctional siiane, or a combination thereof.
• Adhesion promoters are known in the art and may comprise silanes having the formula where each is independently a monovalent organic group
• the adhesion promoter may comprise a partial condensate of the above silane.
• the adhesion promoter may comprise a combination of an alkoxysi!ane and a hydroxy-functional po!yorganosiloxane.
• the adhesion promoter may comprise an unsaturated or epoxy- functionai compound.
• the adhesion promoter may comprise an unsaturated or epoxy- functionai alkoxysilane.
• the functional alkoxysiiane can have the formula
• R ⁇ ⁇ Si(OR ⁇ ) ⁇ ⁇ where subscript t is 1 , 2, or 3, alternatively subscript t is 1.
• Each R 22 j s independently a monovalent organic group with the proviso that at least one is an unsaturated organic group or an epoxy-functional organic group.
• Epoxy-functionai organic groups for R 22 are exemplified by 3-giycidoxypropyl and (epoxycyclohexyl)ethyi.
• Unsaturated organic groups for R 22 are exemplified by 3-methacryloy!oxypropyl, 3- acryioyioxypropyi, and unsaturated monovalent hydrocarbon groups such as vinyl, ailyi, hexertyi, undecy!enyl. Each is independently a saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to2 carbon atoms.
• R ⁇ is exemplified by Me, Et, Pr, and Bu.
• Examples of suitable epoxy-functional alkoxysi!anes include 3- g!ycidoxypropy!trirnethoxysilane, 3-glycidoxypropy!triethoxysilane, (epoxycyclohexyl)ethyidimethoxysilane, (epoxycyciohexyi)ethyidiethoxysilane and combinations thereof.
• Suitable unsaturated alkoxysiianes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysiiane, hexenyltrimethoxysiiane, undecy!enyltrimethoxysi!ane, 3-methacryloyloxypropy! trimethoxysilane, 3- methacryioyloxypropyi triethoxysilane, 3-acryioyioxypropyi trimethoxysilane, 3- acryloyioxypropyl triethoxysilane, and combinations thereof.
• the adhesion promoter may comprise an epoxy-functional siioxane such as a reaction product of a hvdroxy-terminated polvorganosiloxane with an epoxy-functional alkoxysilane, as described above, or a physical blend of the hydroxy- terminated poiyorganosiloxane with the epoxy-functional alkoxysilane.
• the adhesion promoter may comprise a combination of an epoxy-functionai alkoxysilane and an epoxy- functional siioxane.
• the adhesion promoter is exemplified by a mixture of 3- glycidoxypropyltrimethoxysiiane and a reaction product of hydroxy-terminated methylvinylsiioxane with 3-glycidoxypropyltrimethoxysi!ane, or a mixture of 3- g!ycidoxypropyitrimethoxysilane and a hydroxy-terminated methylvinylsiioxane, or a mixture of 3-giycidoxypropyItrimethoxysilane and a hydroxy-terminated methy!viny!/dimethy!si!oxane copolymer.
• the adhesion promoter may comprise an aminofunctional siiane such as an aminofunctional aikoxysiiane exemplified by H 2 N ⁇ CH 2 )2Si(QCH 3 ) 3
• the adhesion promoter may comprise a transition metal chelate.
• Suitable transition metal chelates include titanates, zirconates such as zirconium acetyiacetonate, aluminum chelates such as aluminum acetyiacetonate, and combinations thereof.
• the adhesion promoter may comprise a combination of a transition metal chelate with an aikoxysiiane, such as a combination of g!ycidoxypropy!trimethoxysilane with an aluminum chelate or a zirconium chelate.
• Component (k2) is a release agent.
• Suitable release agents are exemplified by fluorinated compounds, such as fiuoro-functional silicones, or fiuoro-functional organic compounds.
• the surface modifier for component (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 aikyl and aryi groups.
• DOW CORNING® 550 Fluid is a trimethylsiioxy-terminated poIy(dimethyl/methy!pheny!)siloxane with a viscosity of 125 cSt that is commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.
• component (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.
• component (K) depends on various factors including the type of surface modifier selected as component (K) and the end use of the composition and its reaction product. However, component (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. Component (K) may be one adhesion promoter. Alternatively, component (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 iengtheners may include difunctionai silanes and difunctional siloxanes, which extend the length of polyorganosiloxane chains before crossiinking occurs. Chain Iengtheners may be used to reduce the modulus of elongation of the cured product. Chain Iengtheners compete in their reactions with aliphatically unsaturated groups and/or silicon bonded hydrogen atoms in other components of the composition, e.g., components (B) and/or component (C), when present. Dimethylhydrogensiioxy-terminated polydimethylsiloxanes having relatively low degrees of polymerization (e.g., DP ranging from 3 to 50) may be used as component (L). Component (L) may be one chain lengthened Alternatively, component (L) may comprise two or more different chain Iengtheners that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence.
• Component (M) is and endblocker comprising an M-unit, i.e., a siloxane unit of formula ⁇ SiQ ⁇ , where each R 24 independently represents a monovalent, nonfunctional, organic group, such as a monovalent hydrocarbon group free of aliphatic unsaturation.
• Component (M) may comprise poiyorganosiioxanes endbiocked on one terminal end by a triorganosilyl group, e.g., (GH ⁇ SiQ-, and on the other end by a silicon- bonded hydrogen atom and/or an aliphatically unsaturated organic group.
• Component (M) may be a poiydiorganosiloxane such as a po!ydimethylsiioxane.
• the poiydiorganosiloxanes 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 poiydimethy!siloxane 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.
• Component (M) may be one endh!ocker.
• component ( ) 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.
• Component (N) is a flux agent.
• the composition may comprise 0 % to2 % of the flux agent based on the weight of all components 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.
• Component (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 fetramethyl-piperidine derivatives.
• Suitable phenolic antioxidants include vitamin E and IRGANQX 1 - ⁇ 1010 from Ciba Specialty
• IRGANOX® 1010 comprises pentaerythritoi tetrakis(3- ⁇ 3,5-di-t-buty!-4- hydroxyphenyI)propionate).
• UV absorbers include phenol, 2-(2H-benzotriazoi-
• UV stabilizers include bis(1 ,2,2,6,6-pentamethyi-4-piperidyl) sebacate; methyl 1 ,2,2,6, 6-pentamethyl-4- piperidyi/sebacate; and a combination thereof (T!NUVIN® 272).
• T!NUVIN® additives such as T!NUV!N® 765 are commercially available from Ciba Specialty Chemicals of Tarrytown, NY, U.S.A.
• 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
• 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 component (O) depends on various factors including the specific anti-aging additive selected and the anti-aging benefit desired. However, the amount of component (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 ail components in the composition.
• Component (O) may be one anti-aging additive. Alternatively, component (O) may comprise two or more different anti-aging additives.
• Component (P) is a pigment.
• the term 'pigment' includes any component 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 ail components in the composition.
• suitable pigments include indigo, titanium dioxide Stan-Tone 50SP01 Green (which is commercially available from Po!yOne) 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 Eiementis 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.).
• Component (Q) is an acid acceptor. Suitable acid acceptors include magnesium oxide, calcium oxide, and combinations thereof.
• the composition may comprise 0 % to 2 % of component (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 component (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, Disparion from King Industries, Kevlar Fibre Pulp from Du Pont, Rheospan from Nanocor, and Ircogei 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.
• component (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.
• component (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 component (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 chairs, NY, U.S.A.
• SP 96 melting point ranging from 62 °C to 69 °C
• SP 18 melting point ranging from 73 °C to 80 °C
• SP 19 melting point ranging from 76 °C to 83 °C
• SP 26 melting point ranging from 76 °C to 83 °C
• SP 60 melting point ranging from 79 °C to 85 °C
• SP 617 melting point ranging from 88 °C to 93 °C
• SP 89 melting point ranging from 90 °C to 95 °C
• SP 624 melting point ranging from 90 °C to 95 °C
• Multiwax® W-835 which comprises saturated branched and cyclic non-polar hydrocarbons, and has melting point ranging from 73 °C to 80 °C.
• the amount of component (R) depends on various factors including the specific rheological additive selected and the selections of the other components of the composition. However, the amount of component (R) may range from 0 parts to 20 parts, alternatively 1 part to 15 parts, and alternatively 1 part to 5 parts based on the weight of all components in the composition. Component (R) may be one rheo!ogical additive. Alternatively, component (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 components, such as silicone resin.
• Vehicles used herein are those that help f!uidize the components of the composition but essentially do not react with the components.
• the vehicle may be selected based on solubility the components in the composition and volatility.
• the solubility refers to the vehicle being sufficient to dissolve and/or disperse components 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 hydrosilyiation 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 hexamethyldisiioxane, octamethyltrisiloxane, hexamethy!cyclotrisiloxane 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 hexamethyldisiioxane, octamethyltrisiloxane, hexamethy!cyclotrisiloxane 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, isopropanoi, butanol, or n-propanol; a ketone such as acetone, methylethy! ketone, or methyl isobutyi 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, dipropy!ene glycol methyl ether, propylene glycol n-buty! ether, propylene glycol n-propy!
• an alcohol such as methanol, ethanol, isopropanoi, butanol, or n-propanol
• a ketone such as acetone, methylethy! ketone, or methyl isobutyi ketone
• ether or ethylene glycol n-buty! ether, a haiogenated hydrocarbon such as dichloromethane, 1 ,1 , 1-trichioroethane or methylene chloride; chloroform; dimethyl sulfoxide; dimethyl formamide, acetonitri!e; tetrahydrofuran; white spirits; mineral spirits; naphtha; n-methyl pyrrolidone; or a combination thereof.
• a haiogenated hydrocarbon such as dichloromethane, 1 ,1 , 1-trichioroethane or methylene chloride; chloroform; dimethyl sulfoxide; dimethyl formamide, acetonitri!e; tetrahydrofuran; white spirits; mineral spirits; naphtha; n-methyl pyrrolidone; or a combination thereof.
• the amount of vehicle will depend on various factors including the type of vehicle selected and the amount and type of other components 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 components in the composition.
• Component (S) can be added during preparation of the composition, for example, to aid mixing and delivery. All or a portion of component (S) may optionally be removed after the composition is prepared.
• Component (T) is a surfactant.
• Suitable surfactants include silicone po!yethers, 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 % toO.05 % of the surfactant based on the weight of all components in the composition.
• Component (U) is a corrosion inhibitor.
• suitable corrosion inhibitors include benzotriazole, mercaptabenzofriazole and commercially available corrosion inhibitors such as 2,5-dimercapto-1 ,3,4-thiadiazole derivative (CUVAN ⁇ 826) and alky!thiadiazole (CUVAN® 484) from R. T. Vanderbilt of Norwalk, Connecticut, U.S.A.
• the amount of component (U) may range from 0.05 % to 0.5 % based on the weight of the composition.
• components for the composition described above there may be overlap between types of components because certain components described herein may have more than one function.
• certain aikoxysiianes 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.
• the additional components are distinct from one another.
• composition can be prepared by a method comprising combining all components by any convenient means such as mixing at ambient or elevated temperature.
• Component (I) when present, may be added before component (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 component (e.g., filler and/or spacer, if present) with component (G), and thereafter mixing the product thereof with the other components of the composition.
• a particulate component e.g., filler and/or spacer, if present
• the composition may be prepared as a multiple part composition, for example, when component (I) is absent, or when the composition will be stored for a long period of time before use.
• component (A) is stored in a separate part from any component having a silicon bonded hydrogen atom, for example component (C), and the parts are combined shortly before use of the composition.
• a two part composition may be prepared by combining components comprising (B), (A), (F), and optionally one or more other additional components described above to form a base by any convenient means such as mixing.
• a curing agent may be prepared by combining components comprising (B), (C), and optionally one or more other additional components described above by any convenient means such as mixing.
• the components 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 hydrosiiylation reaction to form a reaction product.
• the reaction product may have various forms, such as a siiane, a gum, a gel, a rubber, or a resin.
• P Ar N Me N (1A) refers to the iigand component of Formula (1A) described above, wherein the superscript Ar represents the substituted or unsubstituted arylene group corresponding to X in general formula (1 ), and wherein the superscript Me represents a methyl group corresponding to in general formula (1 ), and wherein Y is an unsubstituted pyridyl group (i.e., wherein no Z superscript is present).
• Ar represents the substituted or unsubstituted arylene group corresponding to X in general formula (1 )
• Me represents a methyl group corresponding to in general formula (1 )
• Y is an unsubstituted pyridyl group (i.e., wherein no Z superscript is present).
• P ⁇ r N ⁇ N ⁇ n (I D) refers to the Iigand component of Formula (1 D) described above, wherein the superscript Pr represents the propylene group corresponding to X in general formula (1 ), and wherein the superscript H represents a hydrogen atom corresponding to R 2 in general formula (1 ), and superscript Ph represents a substituted or unsubstituted phenyl group coupled to the carbon atom in the ring structure adjacent to the nitrogen atom (i.e., wherein Y is a 6-pheny!pyridyl group). In each of these three formulas, because is an unsubstituted phenyl group, this species disappears from the formulas.
• EXAMPLE 1 Preparation and Characterization of PNN Ligands of Formulas (1A)-(1 I)
• a direct synthesis of P ⁇ r N ⁇ N can be synthesized by tempiating directly on a metal to form a stable complex (see synthesis of formula (2G) below for details).
• C0CI2 (81.5 mg, 0.62 mmo!) was dissolved in THF and stirred at room temperature for 1 hour.
• sodium spheres (17.4 mg, 0.76 mmol) and pEtj Hfsj 2QQ m g ( 0.63 mmol) were combined in THF and stirred to give a dark red mixture that is [Na]P ⁇ N ⁇ .
• the ajP ⁇ N ⁇ N solution was filtered through celite into the stirred CoCI 2 solution to give a dark purplish-brown mixture. After 2 hours, this mixture was filtered and solvents were removed under reduced pressure.
• Example 4 ligand components of formulas (1 B), ( E), and (1 H) of the present invention were combined with certain metal precursors and activated with certain ionic activators to form activated reaction products. The activated reaction products were then evaluated for their ability to catalyze hydrosiiyation reactions of 1 -octene with various silanes (HMTS, diphenyisiiane, or triethyisilane).
• HMTS silanes
• Example A In a nitrogen-filled drybox, a scintillation vial was charged with 141 mg (1.26 mmol) of 1 -octene and 1.26 mmol of silane (232 mg, diphenyisiiane). 15 mg
• Examples B and C In a nitrogen-filled drybox, a J Young NMR tube was charged with 139 mg (1 .24 mmol) of 1 -octene and 1 .24 mmol of silane (229 mg, diphenyisiiane). 6.8 mg (0.012 mmol, 1 .0% loading) of the complex
• Example E In a nitrogen-filled drybox, a scintillation vial was charged with 139 mg (1.24 mmol) of 1-octene and 1.24 mmol of silane (143 mg, triethy!silane). 6.8 mg
• Example F in a nitrogen-filled drybox, a scintillation vial was charged with 137 mg (1.22 mmol) of 1 -octene and 1.29 mmol of silane (238 mg, diphenylsiiane). 1.5 mg
• Example G In a nitrogen-filled drybox, a scintillation vial was charged with 139 mg (1.24 mmol) of 1 -octene and 1.24 mmol of silane (275 mg, HMTS). 4.2 mg (0.0090 mmol, 0.7% loading) of the complex Co(P ⁇ ⁇ )(CH 2 SiMe3) n was then added and the reaction was stirred overnight at 25 °C. The reaction was quenched by exposure to air and the product mixture was analysed by NMR spectroscopy. Olefin Conversion > 95%, IO: > 95%.
• Example I In a nitrogen-filled drybox, a scintillation vial was charged with 520 mg of a 1 :1 mixture of 1 -octene: HMTS (1.50 mmol each). 10.0 mg (0.018 mmol, 1.1 % loading) of the complex Fe(P ⁇ r ⁇ ⁇ e )Br2 was then added along with 0.040 mmol of
• Example J In a nitrogen-filled drybox, a scintillation vial was charged with 143 mg (1.27 mmol) of 1 -octene and 1.27 mmol of silane (234 mg, diphenyisilane). 5.0 mg
• Examples K and L in a nitrogen-filled drybox, a J Young NMR tube was charged with 200 mg (1.78 mmol) of 1 -octene and 1.78 mmol of silane (328 mg, diphenyisilane). 8.3 mg (0.013 mmoi, 0.7% loading) of the complex Fe(P Ar N Pn N)Br2 was then added along with 0.040 mmol of NaBEtgH as a toluene solution and 0.2 mL of CgDg and the reaction was stirred at room temperature. The reaction mixture was analysed by NMR spectroscopy. At 30 min AMP: 81 % (Example K), at 2 hours AMP: > 95% (Example L).
• Example M in a nitrogen-filled drybox, a scintillation vial was charged with 520 mg of a 1 : 1 mixture of 1-octene: HMTS (1.50 mmol each). 8.3 mg (0.013 mmol, 0.7% loading) of the complex Fe(P Ar N ⁇ N)Br2 was then added along with 0.030 mmoi of

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