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WO2015023328A1 - Catalyseurs de pyridine diimine de cobalt homogène réutilisable, pour la silylation déshydrogénative et le traitement tandem hydrogénation-silylation déshydrogénative - Google Patents

Catalyseurs de pyridine diimine de cobalt homogène réutilisable, pour la silylation déshydrogénative et le traitement tandem hydrogénation-silylation déshydrogénative Download PDF

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Publication number
WO2015023328A1
WO2015023328A1 PCT/US2014/036935 US2014036935W WO2015023328A1 WO 2015023328 A1 WO2015023328 A1 WO 2015023328A1 US 2014036935 W US2014036935 W US 2014036935W WO 2015023328 A1 WO2015023328 A1 WO 2015023328A1
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group
alkyl
aryl
substituted
unsaturated
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Inventor
Aroop Kumar Roy
Crisita Carmen Hojilla ATIENZA
Paul J. Chirik
Kenrick M. Lewis
Keith J. Weller
Susan Nye
Johannes G.P DELIS
Julie L. Boyer
Tianning DIAO
Eric Pohl
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Princeton University
Momentive Performance Materials Inc
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Princeton University
Momentive Performance Materials Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • 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
    • B01J31/1805—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 the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Definitions

  • This invention relates generally to transition metal-containing compounds, more specifically to cobalt complexes containing pyridine di-imine ligands and their utility as efficient and reusable catalysts for dehydrogenative silylation and tandem dehydrogenative-silylation- hydrogenation.
  • Hydrosilylation chemistry typically involving a reaction between a silyl hydride and an unsaturated organic group, is the basis for synthetic routes to produce commercial silicone -based products like silicone surfactants, silicone fluids and silanes as well as many addition cured products like sealants, adhesives, and silicone -based coating products. See, for example, US Patent Application Publication 2011/0009573A1 to Delis et al.
  • Typical hydrosilylation reactions use precious metal catalysts to catalyze the addition of a silyl-hydride (Si-H) to an unsaturated group, such as an olefin. In these reactions, the resulting product is a silyl-substituted, saturated compound.
  • the addition of the silyl group proceeds in an anti- Markovnikov manner, i.e., to the less substituted carbon atom of the unsaturated group.
  • Most precious metal catalyzed hydrosilylations only work well with terminally unsaturated olefins, as internal unsaturations are generally non-reactive or only poorly reactive.
  • There are currently only limited methods for the general hydrosilylation of olefins where after the addition of the Si- H group there still remains an unsaturation in the original substrate.
  • This reaction termed a dehydrogenative silylation, has potential uses in the synthesis of new silicone materials, such as silanes, silicone fluids, crosslinked silicone elastomers, and silylated or silicone -crosslinked organic polymers such as polyolefins, unsaturated polyesters, and the like.
  • US Patent No. 3,775,452 discloses a platinum complex containing unsaturated siloxanes as ligands. This type of catalyst is known as Karstedt's catalyst.
  • Other exemplary platinum-based hydrosilylation catalysts that have been described in the literature include Ashby's catalyst as disclosed in US Patent No. 3,159,601, Lamoreaux's catalyst as disclosed in US Patent No. 3,220,972 , and Speier's catalyst as disclosed in Speier, J.L, Webster J.A. and Barnes G.H., J. Am. Chem. Soc. 79, 974 (1957).
  • Fe(CO)s to promote limited hydros ilylations and dehydrogenative silylations.
  • the use of Fe 3 (CO)i2 was also found to exhibit dehydrogenative silylation in the reaction of EtsSiH and styrene. (Kakiuchi, F.; Tanaka, Y.; Chatani, N.; Murai, S. J.
  • Allyl silanes could be prepared in high yields using a rhodium complex (Mitsudo, T.; Watanabe, Y.; Hori, Y. Bull. Chem. Soc. Jpn. 1988, 61,
  • Vinyl silanes could be prepared through the use of a rhodium catalyst (Murai, S.;
  • Vinyl silanes could also be produced using ruthenium complexes (Murai, S.; Seki, Y.;
  • US Patent No. 5,955,555 discloses the synthesis of certain iron or cobalt pyridine di- imine (PDI) dianion complexes.
  • the preferred anions are chloride, bromide and
  • US Patent No. 7,442,819 discloses iron and cobalt complexes of certain tricyclic ligands containing a "pyridine" ring substituted with two imino groups.
  • US Patent Nos. 6,461,994, 6,657,026 and 7, 148,304 disclose several catalyst systems containing certain transitional metal-PDI complexes.
  • US Patent No. 7,053,020 discloses a catalyst system containing, inter alia, one or more bisarylimino pyridine iron or cobalt catalyst.
  • the catalysts and catalyst systems disclosed in these references are described for use in the context of olefin polymerizations and/or oligomerisations, not in the context of dehydrogenative silylation reactions.
  • homogeneous metal catalysts suffer from the drawback that following consumption of the first charge of substrates, the catalytically active metal is lost to aggregation and agglomeration whereby its catalytic properties are substantially diminished via colloid formation or precipitation. This is a costly loss, especially for noble metals such as Pt.
  • Heterogeneous catalysts are used to alleviate this problem but have limited use for polymers and also have lower activity than homogeneous counterparts. For example, it is well-known in the art and in the hydrosilylation industry that the two primary homogeneous catalsysts, Speier's and Karstedt's often lose activity after catalyzing a charge of olefin and silyl- or siloxyhydride reaction.
  • the present invention is directed to a process for producing a
  • dehydrogenatively silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, in order to produce the dehydrogenatively silylated product, wherein the catalyst is a complex of the Formula (I) or an adduct thereof;
  • each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, C1-C18 alkyl, a Cl- C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, wherein one or more of R'-R 5 , other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 1 - R 7 vicinal to one another, R'-R 2 , and/or R 4 -R 5 taken together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure, with the proviso that R'-R 7 and R 5 -R 6 are not taken to form a terpyridine ring; and
  • L is hydroxyl, or a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl, or substituted aryl group, wherein L optionally contains at least one heteroatom.
  • the present invention is directed to a compound of Formula (II)
  • each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, C1-C18 alkyl, a Cl- C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, wherein one or more of R'-R 5 , other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 1 - R 7 vicinal to one another, R'-R 2 , and/or R 4 -R 5 taken together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure, with the proviso that R'-R 7 and R 5 -R 6 are not taken to form a terpyridine ring.
  • the present invention is directed to a process for producing a crosslinked material, comprising reacting a reaction mixture comprising (a) a silyl-hydride containing polymer, (b) a mono-unsaturated olefin, or an unsaturated polyolefin or mixtures thereof and (c) a catalyst, optionally in the presence of a solvent, in order to produce the crosslinked material, wherein the catalyst is a complex of the Formula (I) or an adduct thereof;
  • each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, C1-C18 alkyl, a Cl-
  • R 6 and R 7 are independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 1 - R 7 vicinal to one another, R'-R 2 , and/or R 4 -R 5 taken together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure, with the proviso that R'-R 7 and R 5 -R 6 are not taken to form a terpyridine ring; and L is hydroxyl, or a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl, or substituted aryl group,
  • this invention relates to the reusability of a single charge of catalyst for multiple and sequential charges of the unsaturated substrate and SiH compound for dehydrogenative silylation or for tandem hydrogenation of a dehydrogenatively silylated product formed, without the need for additional charges of catalyst.
  • the invention relates to cobalt complexes containing pyridine di-imine ligands and their use as efficient dehydrogenative silylation and crosslinking catalysts.
  • a complex of the Formulae (I) or (II) as illustrated above wherein Co in any valence or oxidation state (e.g., +1, +2, or +3) for use in said dehydrogenative silylation and crosslinking reactions.
  • Co in any valence or oxidation state e.g., +1, +2, or +3
  • a class of cobalt pyridine di-imine complexes has been found that are capable of dehydrogenative silylation reactions.
  • transition metal catalysts based on cobalt- diimine complexes can be reused to catalyze a fresh charge of substrates, or can be re-used to catalyze tandem dehydrogenative-silylation-hydrogentation in the same vessel without the need to isolate or purify the intermediate dehydrogenative silylation product.
  • the stability of the catalysts of the present invention can allow for more efficient industrial silylation processes at lower cost.
  • alkyl herein is meant to include straight, branched and cyclic alkyl groups. Specific and non-limiting examples of alkyls include, but are not limited to, methyl, ethyl, propyl and isobutyl.
  • substituted alkyl herein is meant an alkyl group that contains one or more substituent groups that are inert under the process conditions to which the compound containing these groups is subjected.
  • the substituent groups also do not substantially or deleteriously interfere with the process.
  • aryl herein is meant a non-limiting group of any aromatic hydrocarbon from which one hydrogen atom has been removed.
  • An aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups.
  • Specific and non-limiting examples of aryls include, but are not limited to, tolyl, xylyl, phenyl and naphthalenyl.
  • substituted aryl herein is meant an aromatic group substituted as set forth in the above definition of “substituted alkyl.” Similar to an aryl, a substituted aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group can be to a heteroatom (such as nitrogen) of the heteroaromatic ring instead of a carbon. If not otherwise stated, it is preferred that substituted aryl groups herein contain 1 to about 30 carbon atoms.
  • alkenyl herein is meant any straight, branched, or cyclic alkenyl group containing one or more carbon-carbon double bonds, where the point of substitution can be either a carbon- carbon double bond or elsewhere in the group.
  • alkenyls include, but are not limited to, vinyl, propenyl, allyl, methallyl, ethylidenyl norbornane.
  • alkynyl is meant any straight, branched, or cyclic alkynyl group containing one or more carbon-carbon triple bonds, where the point of substitution can be either at a carbon-carbon triple bond or elsewhere in the group.
  • inert substituent herein is meant a group other than hydrocarbyl or substituted hydrocarbyl, which is inert under the process conditions to which the compound containing the group is subjected.
  • the inert substituents also do not substantially or deleteriously interfere with any process described herein that the compound in which they are present may take part in.
  • examples of inert substituents include halo (fluoro, chloro, bromo, and iodo), ether such as -OR 8 wherein R 8 is hydrocarbyl or substituted hydrocarbyl.
  • hetero atoms herein is meant any of the Group 13-17 elements except carbon, and can include for example oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine.
  • olefin herein is meant any aliphatic or aromatic hydrocarbon also containing one or more aliphatic carbon-carbon unsaturations. Such olefins may be linear, branched or cyclic and may be substituted with heteroatoms as described above, with the proviso that the substituents do not interfere substantially or deleteriously with the course of the desired reaction to produce the dehydrogenatively silylated product.
  • room temperature can refer to a temperature of from about 23 °C to about 30 °C.
  • the present invention is directed to a process for producing a dehydrogenatively silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, in order to produce the dehydrogenative silylated product, wherein the catalyst is a complex of the Formula (I) or an adduct thereof;
  • each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, C1-C18 alkyl, a Cl- C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, wherein one or more of R'-R 5 , other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 1 - R 7 vicinal to one another, R'-R 2 , and/or R 4 -R 5 taken together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure, with the proviso that R'-R 7 and R 5 -R 6 are not taken to form a terpyridine ring; and
  • L is hydroxyl, or a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl, or substituted aryl group, wherein L optionally contains at least one heteroatom.
  • the catalyst utilized in the process of the present invention is illustrated in Formula (I) above wherein Co is in any valence or oxidation state (e.g., +1, +2, or +3).
  • Co is in any valence or oxidation state (e.g., +1, +2, or +3).
  • at least one of R 6 and R 7 is
  • each occurrence of R 9 , R 10 , R 11 , R 12 , and R 13 is independently hydrogen, C1-C18 alkyl, CI -CI 8 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R 9 -R 13 , other than hydrogen, optionally contain at least one heteroatom.
  • R 9 and R 13 may further include independently methyl, ethyl or isopropyl groups and R 11 may be hydrogen or methyl.
  • R 9 , R 11 , and R 13 are each methyl; R 1 and R 5 may
  • R 2 , R 3 and R 4 may be hydrogen.
  • One particularly preferred embodiment of the catalyst of the process of the invention is the compound of Formula (II)
  • each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, C1-C18 alkyl, a ClCI 8 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, wherein one or more of R'-R 5 , other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 1 - R 7 vicinal to one another, R'-R 2 , and/or R 4 -R 5 taken together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure, with the proviso that R'-R 7 and R 5 -R 6 are not taken to form a terpyridine ring.
  • the catalyst is generated in-situ by contacting a catalyst precursor with an activator in the presence of a liquid medium containing at least one component selected from the group consisting of a solvent, the silyl hydride, the compound containing at least one unsaturated group, and combinations thereof, wherein the catalyst precursor is represented by structural Formula (III)
  • each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, C1-C18 alkyl, a Cl- C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, wherein one or more of R'-R 5 , other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 1 - R 7 vicinal to one another, R'-R 2 , and/or R 4 -R 5 taken together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure, with the proviso that R'-R 7 and R 5 -R 6 are not taken to form a terpyridine ring; and
  • X is an anion selected from the group consisting of F “ , CI “ , Br “ , ⁇ , CF 3 R 14 S0 3 _ or
  • R 15 COO " wherein R 14 is a covalent bond or a C1-C6 alkylene group, and R 15 is a C1-C10 substituted or unsubstituted hydrocarbyl group.
  • the activator may be a reducing agent or an alkylating agent such as NaHBEt 3 , CH 3 L1, DIBAL-H, LiHMDS, a Grignard reagent as well as combinations thereof.
  • the reducing agent has a reduction potential more negative than -0.6 v (versus ferrocene, as described in Chem. Rev. 1996, 96, 877-910. A larger negative number represents a larger reduction potential).
  • the reduction potential ranges from -0.76 V to -2.71V.
  • the most preferred reducing agents have a reduction potential in the range of -2.8 to -3.1 V.
  • the catalysts can be prepared by reacting a PDI ligand with a metal halide, such as FeBr 2 as disclosed in US Patent Application Publication 201 1/0009573 Al.
  • a metal halide such as FeBr 2
  • the PDI ligands are produced through condensation of an appropriate amine or aniline with 2,6- diacetylpyridine and its derivatives.
  • the PDI ligands can be further modified by known aromatic substitution chemistry.
  • the catalysts can be unsupported or immobilized on a support material, for example, carbon, silica, alumina, MgCl 2 or zirconia, or on a polymer or prepolymer, for example polyethylene, polypropylene, polystyrene, poly(aminostyrene), or sulfonated polystyrene.
  • a support material for example, carbon, silica, alumina, MgCl 2 or zirconia
  • a polymer or prepolymer for example polyethylene, polypropylene, polystyrene, poly(aminostyrene), or sulfonated polystyrene.
  • the metal complexes can also be supported on dendrimers.
  • R 1 to R 7 of the metal complexes has a functional group that is effective to covalently bond to the support.
  • exemplary functional groups include but are not limited to SH, COOH, NH 2 or OH groups.
  • silica supported catalyst may be prepared via Ring-Opening Metathesis Polymerization (ROMP) technology as discussed in the literature, for example Macromol. Chem. Phys. 2001, 202, No. 5, pages 645-653; Journal of Chromatography A, 1025 (2003) 65-71.
  • REP Ring-Opening Metathesis Polymerization
  • the unsaturated compound containing at least one unsaturated functional group utilized in the process of the invention can be a compound having one, two, three, or more unsaturations.
  • unsaturated compounds include an olefin, a cycloalkene, unsaturated polyethers such as an alkyl-capped allyl polyether, a vinyl-functional alkyl-capped allyl or methallyl polyether, an alkyl-capped terminally unsaturated amine, an alkyne, terminally unsaturated acrylate or methacrylate, unsaturated aryl ether, vinyl-functionalized polymer or oligomer, vinyl-functionalized silane, vinyl-functionalized silicone, unsaturated fatty acids, unsaturated esters, and combinations thereof.
  • unsaturated polyethers such as an alkyl-capped allyl polyether, a vinyl-functional alkyl-capped allyl or methallyl polyether, an alkyl-capped terminally unsaturated amine, an alkyne, terminally
  • Unsaturated polyethers suitable for the dehydrogenative silylation reaction preferably are polyoxyalkylenes having the general formula:
  • R is hydrogen, vinyl, or a polyether capping group of from 1 to 8 carbon atoms such as the alkyl groups: CH 3 , n-C 4 H 9 , t-C 4 H 9 or i-CgHn, the acyl groups such as CH 3 COO, t-C 4 H 9 COO, the beta-ketoester group such as
  • R 18 and R 19 are monovalent hydrocarbon groups such as the CI - C20 alkyl groups, for example, methyl, ethyl, isopropyl, 2-ethylhexyl, dodecyl and stearyl, or the aryl groups, for example, phenyl and naphthyl, or the alkaryl or aralkyl groups, for example, benzyl, phenylethyl and nonylphenyl, or the cycloalkyl groups, for example, cyclohexyl and cyclooctyl.
  • R 19 may also be hydrogen.
  • Methyl is the most preferred R 18 and R 19 groups.
  • Each occurrence of z is 0 to 100 inclusive and each occurrence of w is 0 to 100 inclusive. Preferred values of z and w are 1 to 50 inclusive.
  • preferred unsaturated compounds useful in the process of the present invention include ⁇ , ⁇ -dimethylallyl amine, allyloxy-substituted polyethers, propylene, 1-butene, 1-hexene, styrene,, vinylnorbornane, 5-vinyl-norbornene, long-chain, linear alpha olefins such as 1 -octadecene, internal olefins such as cyclopentene, cyclohexene, norbornene, and 3-hexene, branched olefins such as isobutylene and 3 -methyl- 1-octene, unsaturated polyolefins, e.g., polybutadiene, polyisoprene and EPDM, unsaturated acids or esters such as oleic acid, linoleic acid and methyl oleate, a vinyl siloxane of the Formula (VII), and combinations thereof,
  • each occurrence of R is independently a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, vinyl, C3-C18 terminal alkenyl, aryl, or a substituted aryl, and n is greater than or equal to zero.
  • internal olefin means an olefin group not located at a chain or branch terminus, such as 3-hexene.
  • the silyl hydride employed in the reaction is not particularly limited. It can be any compound selected from the group consisting of R a SiH 4 _ a , (RO) a SiH 4 _ a , Q u T v T p H D w D H x M H y M z , and combinations thereof.
  • the silyl hydride can contain linear, branched or cyclic structures, or combinations thereof.
  • each occurrence of R is independently CI -CI 8 alkyl, Cl- CI 8 substituted alkyl, wherein R optionally contains at least one heteroatom, each occurrence of a independently has a value from 1 to 3, each of p, u, v, y and z independently has a value from 0 to 20, w and x are from 0 to 500, provided that p + x + y equals 1 to 500 and the valences of the all the elements in the silyl hydride are satisfied.
  • p, u, v, y, and z are from 0 to 10
  • w and x are from 0 to 100, wherein p+ x + y equals 1 to 100.
  • an "M” group represents a monofunctional group of formula R' 3 SiOi /2
  • a "D” group represents a difunctional group of formula R' 2 Si0 2/2
  • a "T” group represents a trifunctional group of formula R'Si0 3/2
  • a "Q” group represents a tetrafunctional group of formula Si0 4/2
  • an "M H " group represents HR' 2 SiOi /2
  • a "T H " represents HSi0 3/2
  • a "D H " group represents R'HSi0 2/2 .
  • Each occurrence of R' is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, wherein R' optionally contains at least one heteroatom.
  • silyl hydrides containing at least one silylhydride functional group include
  • the silyl hydride has one of the following structures:
  • the catalysts of the invention are useful for catalyzing dehydrogenative silylation reactions.
  • an appropriate silyl hydride such as triethoxysilane
  • the reactions are typically facile at ambient temperatures and pressures, but can also be run at lower or higher temperatures (0 to 300°C) or pressures (ambient to 3000 psi).
  • a range of unsaturated compounds can be used in this reaction, such as ⁇ , ⁇ -dimethylallyl amine, allyloxy- substituted poly ethers, cyclohexene, and linear alpha olefins (i.e., 1 -butene, 1 -octene, 1- dodecene, etc.).
  • the catalyst is capable of first isomerizing the olefin, with the resulting reaction product being the same as when the terminally-unsaturated alkene is used.
  • the reaction can give a bis- substituted silane, where the silyl groups are in the terminal positions of the compound, and there is still an unsaturated group present in the product.
  • a second silane may be added to produce an asymmetrically substituted bis-silyl alkene.
  • the resulting silane is terminally substituted at both ends.
  • This bis-silane can be a useful starting material for the production of alpha, omega -substituted alkanes or alkenes, such as diols and other compounds easily derived from the silylated product. Long chain alpha, omega-substituted alkanes or alkenes are not easily prepared today, and could have a variety of uses for preparing unique polymers (such as polyurethanes) or other useful compounds.
  • a singly-unsaturated olefin may be used to crosslink silyl-hydride containing polymers.
  • a silyl-hydride polysiloxane such as SL6020 (MDi 5 D H 3 0 M)
  • 1-octene in the presence of the cobalt catalysts of this invention to produce a crosslinked, elastomeric material.
  • a variety of new materials can be produced by this method by varying the hydride polymer and length of the olefin used for the crosslinking.
  • the catalysts used in the process of the invention have utility in the preparation of useful silicone products, including, but not limited to, coatings, for example release coatings, room temperature vulcanizates, sealants, adhesives, products for agricultural and personal care applications, and silicone surfactants for stabilizing polyurethane foams.
  • this invention also provides for tandem hydrogenation of the unsaturated product to saturated species simply via introducing hydrogen gas into the reaction vessel following the dehydrogenative silylation reaction.
  • the dehydrogenative silylation may be carried out on any of a number of unsaturated polyolefins, such as polybutadiene, polyisoprene or EPDM-type copolymers, to either functionalize these commercially important polymers with silyl groups or crosslink them via the use of hydros iloxanes containing multiple SiH groups at lower temperatures than conventionally used. This offers the potential to extend the application of these already valuable materials in newer commercially useful areas.
  • the catalysts are useful for dehydrogenative silylation of a composition containing a silyl hydride and a compound having at least one unsaturated group.
  • the process includes contacting the composition with a metal complex of the catalyst, either supported or unsupported, to cause the silyl hydride to react with the compound having at least one unsaturated group to produce a dehydrogenative silylation product, which may contain the metal complex catalyst.
  • the dehydrogenative silylation reaction can be conducted optionally in the presence of a solvent. If desired, when the dehydrogenative silylation reaction is completed, the metal complex can be removed from the reaction product by magnetic separation and/or filtration. These reactions may be performed neat, or diluted in an appropriate solvent. Typical solvents include benzene, toluene, diethyl ether, etc. It is preferred that the reaction is performed under an inert atmosphere.
  • the catalyst can be generated in-situ by reduction using an appropriate reducing agent.
  • the catalyst complexes of the invention are efficient and selective in catalyzing dehydrogenative silylation reactions.
  • the reaction products are essentially free of unreacted alkyl- capped allyl polyether and its isomerization products.
  • the reaction products do not contain the unreacted alkyl-capped allyl polyether and its isomerization products.
  • the dehydrogenatively silylated product is essentially free of internal addition products and isomerization products of the unsaturated amine compound.
  • essentially free is meant no more than 10 wt%, preferably 5 wt% based on the total weight of the hydrosilylation product.
  • Essentially free of internal addition products is meant that silicon is added to the terminal carbon.
  • the catalysts of the present invention offer two additional advantages.
  • First, the catalysts of the present invention are not destroyed during the catalytic processes outlined above.
  • the stability of these catalysts allows them to be used multiple times without loss of catalytic activity.
  • Second, the catalysts of the present invention can be re -used to catalyze tandem
  • the catalysts of the present invention it is possible to use the catalysts of the present invention to perform dehydrogenative silylation of a composition containing a silyl hydride and a compound having at least one unsaturated group as described above, and then subsequently add hydrogen gas directly to the reaction vessel to effect a hydrogenation reaction using the same catalyst. This allows the flexibility to generate a dehydrogenatively silylated product or a saturated product in the same vessel without the need to transfer to another vessel or use another catalyst.
  • the catalyst loading can be chosen as desired for a particular purpose or intended application.
  • the catalyst is present in an amount of from about 0.1 mol% to about 5 mol%; from about 0.5 mol% to about 3 mol%; even from about 1 mol% to about 5 mol%.
  • numerical values can be combined to form new and non-disclosed or non-specified ranges.
  • the catalyst loadings expressed as mol% of the cobalt complex are based on the moles of cobalt complex in relation to the moles of unsaturated compound and can be evaluated expressed by (molco complex mo l 0 i e fm x 100).
  • GC analyses were performed using a Shimadzu GC-2010 gas chromatograph equipped with a Shimadzu AOC-20s autosampler and a Shimadzu SHRXI-5MS capillary column (15m x 250 ⁇ ).
  • the instrument was set to an injection volume of 1 ⁇ L, an inlet split ratio of 20: 1, and inlet and detector temperatures of 250°C and 275°C, respectively.
  • UHP-grade helium was used as carrier gas with a flow rate of 1.82 mL/min.
  • the temperature program used for all the analyses is as follows: 60 °C, 1 min; 15 °C/min to 250 °C, 2 min.
  • Example 1 Synthesis of ( Mes PDI)CoN 2 .
  • This compound was prepared in a manner similar to the synthesis of ( iPr PDI)CoN 2 (Bowman, supra) with 0.500 g (0.948 mmol) of ( Mes PDI)CoCl 2 , 0.1 10 g (4.75 mmol, 5.05 equiv) of sodium and 22.0 g (108 mmol, 1 14 equiv) of mercury.
  • Example 2 Synthesis of ( Mes PDI)CoOH.
  • a 20mL scintillation vial was charged with 0.100 g (0.203 mmol) of ( Mes PDI)CoCl, 0.012 g (0.30 mmol, 1.5 equiv) of NaOH, and approximately 10 mL THF.
  • the reaction was stirred for two days upon which the color of the solution changed from dark pink to red. THF was removed in vacuo and the residue was dissolved in
  • Example 3 Silylation of 1-octene with MD M using various Co complexes.
  • a scintillation vial was charged with 0.100 g (0.891 mmol) of 1-octene and 0.009 mmol (1 mol%) of the cobalt complex (see Table 1 for specific amounts).
  • 0.100 g (0.449 mmol, 0.50 equiv) of MD H M was then added to the mixture and the reaction was stirred at room temperature for one hour/24 hours. The reaction was quenched by exposure to air and the product mixture was analyzed by gas chromatography and NMR spectroscopy.
  • Example 4 Silylation of 1-octene with different silanes using ( es PDI)CoCH 3 and
  • Example 5 In situ Activation of Cobalt Pre-catalysts.
  • a 20mL scintillation vial was charged with 0.100 g (0.891 mmol) of 1 -octene, 0.100 g (0.449 mmol) MD H M and 0.005 g (0.009 mmol, 1 mol%) of ( Mes PDI)CoCl 2 .
  • Example 7 Silylation of 1-octene with MD M using ( Mes PDI)CoCH 3 in the presence of H 2 .
  • Example 8 Silylation of 1-butene with different silanes using ( es PDI)CoCH 3 .
  • a thick- walled glass vessel was charged with 0.449 mmol of the silane (0.100 g MD H M, 0.075 g
  • Example 9 Silylation of TBE with MD M using ( Mes PDI)CoCH 3 . This reaction was carried out in a manner similar to the silylation of 1-butene using 0.100 g (0.449 mmol) of MD H M, 0.004 g (0.009 mmol) of ( Mes PDI)CoCH 3 and 0.891 mmol of TBE.
  • Example 12 Crosslinking of M vl D i2 oM vl (SL 6100) and MD i5 D 30 M (SL 6020) at room temperature.
  • a scintillation vial was charged with 1.0 g of M vl Di 20 M vl (SL 6100) in which M vl is vinyl dimethyl SiO, and 0.044 g of MDi 5 D H 30 M (SL 6020).
  • a solution of the catalyst was prepared by dissolving 0.010 g of ( Mes PDI)CoCH 3 or ( Mes PDI)CoN 2 in
  • Example 13 Crosslinking of M vi D 120 M vi (SL 6100) and MD 15 D H 30 M (SL 6020) at 65 °C.
  • Example 14 Silylation of l-bis(trimethylsiloxy)methylsilyl-2-octene with MD H M using ( Mes PDI)CoCH 3 .
  • This experiment was performed in a manner similar to the silylation of 1 - octene using 0.100 g (0.301 mmol) of l-bis(trimethylsiloxy)methylsilyl-2-octene, 0.034 g (0.152 mmol, 0.51 equiv) of MD H M, and 0.001 g (0.002 mmol, 1 mol%) of ( Mes PDI)CoCH 3 .
  • the reaction was stirred at room temperature for 24 hours and quenched by exposure to air.
  • Example 15 Alternative procedure for the double silylation of 1-octene with MD H M using ( Mes PDI)CoCH 3 .
  • This experiment is performed in a manner similar to the silylation of 1-octene using 0.100 g (0.891 mmol) of 1-octene, 0.150 g (0.674 mmol, 0.756 equiv) of MD H M and 0.004 g (0.008 mmol, 1 mol%) of ( Mes PDI)CoCH 3 .
  • the reaction was stirred at room temperature for 24 hours and quenched by exposure to air.
  • This experiment was performed in a manner similar to the silylation of 1- bis(trimethylsiloxy)methylsilyl-2-octene using 0.100 g (0.361 mmol) of 1- bis(trimethylsiloxy)methylsilyl-2-butene, 0.040 g (0.18 mmol, 0.50 equiv) of MD H M and 0.002 g (0.004 mmol, 1 mol%) of ( Mes PDI)CoCH 3 . The reaction was stirred for 24 hours and quenched by exposure to air.
  • Example 17A-17F Crosslinking of polysiloxanes with olefins using ( Mes PDI)CoCH 3 .
  • Each of the hexane-extracted samples was analyzed by nuclear magnetic resonance (NMR) spectroscopy on a Bruker AVANCE 400WB Spectrometer operating at field strength of 9.40T; 'H's resonate at 400 MHz.
  • Single pulse excitation (SPE) pulse sequence with magic angle spinning (MAS) was used with a delay of 150 seconds for the ⁇ 'H- ⁇ Q SPE/MAS NMR spectra or a delay of 300 seconds for the ⁇ 'H- ⁇ Si ⁇ SPE/MAS NMR spectra.
  • Cross-polarization (CP) pulse sequence with magic angle spinning (MAS) was used with a delay of 10 seconds and a contact time of 5 ms for the ⁇ 'H- ⁇ C ⁇ CP/MAS NMR spectra.
  • ⁇ SiCH 2 CH 2 CH CH(CH 2 ) 2 CH 2 CH 2 CH 3 .
  • the two signals observed at ⁇ 125 and 5 131 due to the olefinic carbons are found with approximate equal intensity.
  • the signals are consistent with the double bond being in position 2 or 6.
  • the CP data for sample 18A show a very weak peak observed at ⁇ 14 indicating that if the double bond is in position 6 the major configuration must be trans.
  • the weaker signals observed around ⁇ 130 are consistent with the double bond being in position 3, 4, or 5.
  • the SPE and CP data show significant loss in peak area for the CH 2 , CH 3 , and olefinic carbons.
  • the methyl group is farther from the point of cross-linking.
  • MDi5D H 3 oM show a large amount of what could be a combination of cyclic D3 and D 1 type species and do not contain a signal at ⁇ -35.
  • Examples 18A - 18B These Examples illustrate deuterium labeling experiments that were done to establish that the occurrence of dehydrogenative hydros ilylation when the reaction of hydridosiloxanes and olefins is catalyzed by ( Mes PDI)CoCH 3.
  • Example 18A Silylation of 1-octene with (OTMS) 2 CH 3 Si-D (MD H M- ⁇ ).
  • This reaction was performed in a manner similar to the silylation of 1 -octene with MD H M using 0.050 g (0.45 mmol) of 1-octene, 0.050 g (0.22 mmol, 0.5 equiv) ⁇ ⁇ ⁇ - ⁇ , (70% deuterated), and 0.002 g (0.004 mmol, 1 mol%) of ( Mes PDI)CoCH 3 .
  • the reaction was quenched after stirring for one hour at room temperature.
  • Example 19A shows that ( Mes PDI)CoCH 3 does not isomerize 1-octene.
  • Example 19B shows that 1-octene isomerization was not observed with ( Mes PDI)CoCH 3 and trace amounts of hydridotrisiloxane, MD H M.
  • Example 21 A This experiment was performed in the same manner as the experiment described above (Example 21 A) using 0.100 g (0.891 mmol) of 1-octene, 0.004 g (0.008 mmol, 1 mol%) of ( Mes PDI)CoCH 3 , and 0.014 g (0.063 mmol, 7 mol%) of MD H M.
  • the 3 ⁇ 4 NMR spectrum of the product showed only 1-octene, traces of free ligand and l-bis(trimethylsiloxy)methylsilyl-2- octene, and no evidence for olefin isomerization.
  • Example 20A - 20C Silylation of propylene with different silanes using ( Mes PDI)CoCH 3 .
  • This reaction was carried out in a manner similar to the silylation of 1 -butene using 0.1 1 mmol of silane (0.025 g of MD H M, 0.018 g of (EtO) 3 SiH or 0.015 g of (OEt) 2 CH 3 SiH) 0.001 g (0.002 mmol) of ( Mes PDI)CoCH 3 and 5.6 mmol (50 equiv) of propylene.
  • the non-volatiles were analyzed by NMR spectroscopy.
  • Example 24 Reusability of the initial charge of ( Mes PDI)CoMe for catalysis.
  • a 20mL scintillation vial was charged with 0.100 g (0.891 mmol) of 1-octene and 0.100 (0.449 mmol) of MD H M. 0.001 g (0.002 mmol) of ( Mes PDI)CoMe was then added, and the reaction was stirred at room temperature. An aliquot of the reaction was analyzed by GC after 30min, which established complete conversion of the substrates to the allylsilane product. The reaction vial containing the allylsilane product was then charged with another 0.100 g of 1- octene and 0.100 g of MD H M. Complete conversion (based on GC analysis) of the second batch of substrates was observed after stirring the reaction for one hour at room temperature.

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Abstract

L'invention concerne des complexes de cobalt contenant des ligands de pyridine diimine tridentés et leur utilisation comme catalyseurs efficaces et réutilisables, de silylation déshydrogénative sélective, de réticulation et de traitement tandem hydrogénation-silylation déshydrogénative.
PCT/US2014/036935 2013-08-14 2014-05-06 Catalyseurs de pyridine diimine de cobalt homogène réutilisable, pour la silylation déshydrogénative et le traitement tandem hydrogénation-silylation déshydrogénative Ceased WO2015023328A1 (fr)

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US9381506B2 (en) 2013-11-19 2016-07-05 Momentive Performance Materials Inc. Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation
US9387468B2 (en) 2013-11-19 2016-07-12 Momentive Performance Materials Inc. Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation
EP3071583B1 (fr) * 2013-11-19 2018-05-09 Momentive Performance Materials Inc. Silylation déshydrogénante, hydrosilylation et réticulation à l'aide de catalyseurs au cobalt
CN111286033A (zh) * 2020-02-11 2020-06-16 合肥盖特环保技术有限责任公司 一种接枝聚硅烷类闪烁体及其制备方法

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9371340B2 (en) 2012-08-16 2016-06-21 Momentive Performance Materials Inc. Dehydrogenative silylation, hydrosilylation and crosslinking using cobalt catalysts
US9381506B2 (en) 2013-11-19 2016-07-05 Momentive Performance Materials Inc. Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation
US9387468B2 (en) 2013-11-19 2016-07-12 Momentive Performance Materials Inc. Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation
EP3071583B1 (fr) * 2013-11-19 2018-05-09 Momentive Performance Materials Inc. Silylation déshydrogénante, hydrosilylation et réticulation à l'aide de catalyseurs au cobalt
CN111286033A (zh) * 2020-02-11 2020-06-16 合肥盖特环保技术有限责任公司 一种接枝聚硅烷类闪烁体及其制备方法
CN111286033B (zh) * 2020-02-11 2022-02-18 合肥盖特环保技术有限责任公司 一种接枝聚硅烷类闪烁体及其制备方法

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